中文   |   English   |   Email Alert
Fig/Tab
Advanced Search
image

Metal Oxalate-Based Anode Materials: A New Choice for Energy Storage Materials Applied in Metal Ion Batteries

Geng Gao , Keyu Zhang , Qianwen Wang , Libo Zhang , Dingfang Cui , Yaochun Yao

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 434 -446.

PDF
Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 434-446 DOI: 10.7536/PC210108
research-article
Scan to read & Share
Metal Oxalate-Based Anode Materials: A New Choice for Energy Storage Materials Applied in Metal Ion Batteries
Author information +
History +
PDF

Abstract

Recently, the capacities and energy densities of graphite anode material and lithium transition metal oxide cathode materials for commercial lithium ion batteries are approaching their theoretical values. Exploring the next generation of high-energy density electrode materials is the key factor to solve the capacity limitation of lithium ion batteries at the present stage. New metal oxalate-based anode materials have been considered as a kind of green energy storage material with broad application prospects in metal ion batteries by virtue of the high energy density and excellent cycling stability with the aid of their diversified energy storage mechanism. In this paper, we review the latest research on metal oxalate-based anode materials in lithium, sodium and potassium metal ion batteries, and emphatically introduce their crystal structures, diversified energy storage mechanism and dynamics characteristics in the process of energy storage. The problems existing in electrochemical energy storage of materials are briefly described and their modification strategies based on controlling of crystal structure and morphology, interface carbon composite and metal elements doping are analyzed. Furthermore, the development direction of metal oxalate-base anode materials in alkali metal (Li, Na, K) ion battery system is predicted.

Contents

1 Introduction

2 Structural characterization of metal oxalate

3 Application in lithium ion batteries

3.1 Traditional lithium storage mechanism

3.2 Novel lithium storage mechanism

3.3 Lithium storage kinetics of metal oxalate based materials

3.4 Modification strategy of electrochemistry property

4 Application in other metal ion batteries

4.1 Sodium-ion batteries

4.2 Potassium ion batteries

5 Conclusion and outlook

Graphical abstract

Keywords

metal oxalate / metal ion battery / energy storage mechanism / modification strategy

Cite this article

Download citation ▾
Geng Gao, Keyu Zhang, Qianwen Wang, Libo Zhang, Dingfang Cui, Yaochun Yao. Metal Oxalate-Based Anode Materials: A New Choice for Energy Storage Materials Applied in Metal Ion Batteries. Progress in Chemistry, 2022, 34(2): 434-446 DOI:10.7536/PC210108

登录浏览全文

4963

注册一个新账户 忘记密码

1 Introduction

The global energy crisis and climate warming have inspired people to pay close attention to and think about the sustainable development of energy[1,2]. Wind energy and solar energy, as the main force of clean new energy, how to efficiently convert and store this part of clean energy is still a serious challenge. As a kind of chemical energy storage devices, batteries have evolved from traditional primary irreversible batteries to lead-acid batteries, nickel-metal hydride batteries and lithium-ion batteries which can store energy repeatedly[3]. Among them, the graphite negative lithium-ion battery with insertion lithium storage mechanism has rapidly become a leader in the field of commercial batteries because of its unique advantages of high energy density, power density, no memory effect and green environmental protection[4,5]. In addition, titanium-based compounds with the same lithium storage mechanism, such as lithium titanate and titanium dioxide, have high lithium intercalation potential, good safety, small volume change (< 4%) and high capacity retention, but their low electronic conductivity (~10-18~10-13S·cm-1) and lithium ion diffusion rate (~10-18~10-13cm2·s-1) greatly limit their rate performance[6][7,8]. Although intercalation anode materials have led lithium-ion batteries into a period of rapid development, the low theoretical capacity of graphite anode is difficult to meet the needs of the next generation of high-energy density lithium-ion batteries for high-capacity anode.
At present, the potential anode materials for lithium-ion batteries can be divided into the following categories according to the different lithium storage mechanisms: (1) Alloying materials, such as phosphorus-based and silicon-based materials, which have low lithium intercalation potential and high theoretical reversible capacity, and can be assembled with the current mainstream commercial cathode materials to form batteries with higher energy and power density[9][10]. However, the intercalation of a large amount of lithium brings obvious volume effect, which easily causes the pulverization of electrode materials and the electrical isolation of active materials, resulting in significant capacity loss, such as the volume expansion rate of Si is as high as ~ 360%[11]. (2) Conversion type anode materials, mainly including metal oxides, carbonates, oxalates, hydroxides, etc[12⇓⇓⇓⇓⇓⇓⇓⇓⇓~22][22⇓⇓~25][26⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~39][40⇓⇓⇓⇓~45]. It can be seen from fig. 1 that different types of anode materials can output lithium storage capacities of hundreds to thousands of milliamperes per gram in the 0~2.5 V(vs Li/Li+) potential range. Compared with the intercalation type and alloying type anode materials, the conversion type anode material has higher reversible capacity, efficient cycle stability, lower volume change rate and proper lithium intercalation potential,It can effectively inhibit the formation of lithium dendrites, improve the safety of lithium ion batteries, and is a green recyclable anode material with great potential for metal ion batteries.
As a new member of conversion anode materials, nanoscale metal oxalate-based materials exhibit high lithium storage capacity and outstanding rate performance in lithium-ion batteries, even exceeding their corresponding metal oxides, although the reasons are still unclear. The excellent lithium storage capacity of transition metal oxalates can not be separated from their diversified energy storage mechanisms. In the first discharge process, divalent transition metal ions were released from the oxalate matrix to form nano-dispersed metal particles, and the non-aqueous electrolyte decomposed to form a layer of solid electrolyte interface (SEI) phase on the surface of the material particles at the interface between the electrode and the electrolyte[36,38,46]. During the charging process, lithium ions are released from the lithium oxalate matrix, possibly due to the high surface energy and catalytic effect of the nano-metal particles, which increase the reversibility of lithium oxalate. At the same time, the nano-metal loses electrons and forms a transition metal oxalate phase with poor crystallinity[36]. According to the conversion type lithium storage mechanism, the anhydrous transition metal oxalate material can release 350~375 mAh·g-1 theoretical specific capacity[28]. However, actual tests have found that transition metal oxalate anode materials generally have an additional capacity of 2-3 times higher than the theoretical capacity, so they are also accompanied by an "unusual" capacity growth phenomenon[35,47].
In this paper, the energy storage mechanism of metal oxalate-based anode materials, especially the energy storage characteristics of hydrous metal oxalate-based materials, was systematically reviewed from the crystal structure of metal oxalate based materials, and the electrochemical performance of the materials in the process of energy storage was briefly summarized.The existing problems of metal oxalate-based anode materials were analyzed and the corresponding solutions were put forward. Finally, the development direction of metal oxalate-based anode materials in alkali metal ion battery system was predicted.

2 Crystal Structure Characteristics of Oxalate Materials

Oxalate is widely distributed in nature and organic life[48,49]. The common oxalates MC2O4·2H2O(M=Mn, Fe, Co, Ni, Cu, Zn) are mostly crystalline solids or amorphous powders, which are insoluble in water. The :Maqn++n/2C2O42-→M(C2O4)n/2·xH2O of the precipitation reaction in aqueous solution is generally followed as follows[50,51]. The solubility product constants of divalent metal oxalates are generally distributed between the 10-15~10-5[50]. All oxalate salts are soluble in acid, and when oxalic acid is in excess, M(C2O4)n/2·xH2O can combine with C2O42- to form charged complex ions[50,51]. In particular, FeC2O4·2H2O can also be transformed into metastable Fe2(C2O4)(OH)2 minerals by 2[FeC2O4·2H2O]→Fe2(C2O4)(OH)2+2H2O+H2C2O4[52].
Common divalent transition metal oxalates MC2O4·2H2O(M=Mn, Fe, Co, Ni, Zn) are often crystallized and precipitated in α-monoclinic and β-orthorhombic systems in solution, as shown in Figure 2[37,53]. In that unit cell, the metal ion coordinate with the oxalate ion to form a 1D infinite chain parallel to the [010] crystal orientation; The 1D chain structure in the [100] crystal is connected by hydrogen bonds generated by water molecules coordinated with metal ions. The difference between α and β crystal forms is mainly reflected in the [001] crystal direction, and the hydrogen bond rearrangement occurs when the β crystal form forms a layered structure perpendicular to the c-axis of the unit cell, resulting in a slight interchain slip along the [010] direction[28,36,38,55]. The β crystal form belongs to the thermodynamic metastable state, and the β crystal phase oxalate can be transformed into the α crystal phase by changing the experimental parameters (temperature, reaction time, reactant concentration)[55,56]. As shown in Fig. 2C, our research group found that at room temperature, with the increase of oxalate ion concentration in the reaction system, β-phase ferrous oxalate was irreversibly converted to α-phase ferrous oxalate[57]. At the same time, this study also found that the existence of [Fe(C2O4)x]-2(x-1) of oxalate complex ions can effectively promote the formation of stable hydrogen bonds in the crystal and promote the phase transformation of ferrous oxalate[57].
As shown in fig. 2e, it has also been reported that a γ-MnC2O4·2H2O (orthorhombic system) exists in the MnC2O4·2H2O in addition to the α and β crystal forms[58]. In the crystal structure, the oxalate ligand has one unbonded oxygen atom and one oxygen atom coordinated to two metal ions. The metal ion is coordinated by four oxygen atoms in two trans-water molecules and three oxalates, forming a long chain of MnO6 octahedra shared along the c-axis angle of the unit cell. In different crystal structures, the distance between atoms is different, and the force between atoms is also different. In addition, the molecular dynamics calculation of α and β phases of ferrous oxalate by our group shows that the hydrogen bonding force is weaker than that in β-FeC2O4,α-FeC2O4, and the Fe — O and C — O bonds in 1D chain structure are stronger[36]. However, the strong hydrogen bonds and the weak interatomic forces between Fe — O and C — O atoms in the β-FeC2O4 are likely to cause the fracture and collapse of the layered structure after the removal of crystal water. A simple low-temperature heat treatment can destroy the hydrogen bonds in the metal oxalate material containing crystal water, thereby obtaining the porous anhydrous oxalate material with similar morphology to the hydrated oxalate materials.

3 Applications in Lithium Ion Batteries

3.1 Traditional lithium storage mechanism of metal oxalate-based material

3.1.1 Metal oxalate material containing crystal water

The research on metal oxalate materials as the anode of lithium-ion batteries began with the report of Tirado et al. In 2008[46]. They point out that both ferrous oxalate materials containing crystalline water and anhydrous materials can be used for reversible lithium storage. However, in the follow-up studies, the specific physical and chemical behavior of crystal water in the process of lithium storage is rarely mentioned. In terms of physical properties, simply from the perspective of the unit cell structure of dihydrate transition metal oxalate, the crystal water in the material should be conducive to maintaining the stability of the unit cell structure of the material during cycling. By comparing the structural characteristics of ferrous oxalate (FeC2O4·xH2O,x∈[0,2]) with different crystal water contents, our research group found that when the crystal water content is high, the material has more stable layered structure maintenance and wider interlayer spacing, relying on stronger Fe-O ionic bonds and interlayer hydrogen bonds[37]. When the content of crystal water is low, the uneven stress distribution in the material is easy to cause the generation of the transverse slip stress (r2) along the c-axis direction and the oblique slip stress (r3) along the (202) crystal plane direction, thus causing the structural fracture phenomenon, as shown in Figure 3. In terms of electrochemical performance, Oh et al. Found that compared with NiC2O4 materials, nickel oxalate dihydrate anode material NiC2O4·2H2O has better electrochemical performance, and the existence of crystal water is conducive to the formation of stable SEI interface[59]. At the same time, they used ex situ XRD and TEM electron diffraction probes to analyze the NiC2O4·2H2O/rGO electrode materials under different charge-discharge conditions, and found that metal Ni was produced during the discharge process, and the nickel oxalate dihydrate electrode materials still retained the original lattice structure after 100 cycles. In addition, the reversible generation of nickel oxalate and lithium oxalate was explained by the interconversion between the NiCO+ fragment and the NiC4O+ fragment displayed by the electrode ToF-SIMS data after cycling. It is noteworthy that they pointed out that the change of binding energy of C element in XPS spectrum also confirmed the formation of lithium oxalate. Recently, Yao et al. also found that FeC2O4·xH2O materials can generate Li2Fe(C2O4)2·2H2O and Fe[H2O]2 by electrochemical reaction with Li+ in the potential range of 0 ~ 3 V, as shown in Figure 4[37]. They proposed that the presence of water of crystallization may inhibit the electrochemical activity of the nanoscale compounds. In addition, Zhang et al. reported the generation of LiOH, Li2C2O4, and Co metal nanoparticles during the first lithium storage process in the CoC2O4·2H2O anode material[60]. With the reduction of the potential, the oxalate radical matrix is further reversibly decomposed to form Li2O and LixC2(x=0~2) compounds under the catalysis of the nano metal cobalt particles; During the charging process, LixC2 and Li2O were reversibly converted to Li2C2O4 and CoO, respectively. Lithium storage similar to this process has also been observed in copper oxalate-based electrode materials containing "zeolite-type" crystal water. Kang et al of Shandong University reported that the crystal water of CuC2O4·xH2O materials was irreversibly consumed and the oxalate was decomposed during the first discharge[30]. Most of the Cu element exists in the form of Cu2O and Cu, and a small part of it exists in the form of amorphous copper oxalate. The electrochemical reaction between Cu and Cu2O and Li2O maintains the high reversible capacity of the material. Noticing the unique lithium storage mechanism of this material, our research group prepared Fe2/3Cu1/3C2O4·xH2O/MWCNTs composite materials by double compounding of copper oxalate, carbon nanotubes and ferrous oxalate, and used the differential electrochemical behavior of hydrous ferrous oxalate and cupper o xalate.The electrochemical activity of the ferrous oxalate dihydrate material for lithium storage is significantly improved by virtue of the copper salt derivatives (Cu2O, Cu, Li2CuO2, and the like) with higher conductivity formed in situ by the copper oxalate material in the first few cycle periods[61].

3.1.2 Metal oxalate material without crystal water

Anhydrous metal oxalate-based materials, as a novel conversion-type anode material, are characterized by multi-phase interconversion in the lithium storage process, which involves the deintercalation of lithium ions in the lattice of the material, the reduction of metal ions to metallic state and the generation of lithium oxalate. The electrochemical reaction of lithium storage is as follows[32,33].
MC2O4 + Li → M + Li 2C2O4 (M = Mn, Fe, Co, Ni)
At the same time, the first discharge process is accompanied by the irreversible transformation of metal oxalate from crystalline state to amorphous state and the irreversible decomposition of electrolyte to form SEI at the electrode-electrolyte interface, as shown in Figure 5A[36,46]. It is worth noting that the change process is consistent with the irreversible capacity loss change during the cycle[28].
In 2008, Tirado et al. Reported the electrochemical reaction of ferrous oxalate electrode material in ethylene carbonate-diethyl carbonate electrolyte solution dissolved with LiPF6[46]. They used Fe-selective spectroscopy to observe electrode materials in different charge-discharge States and found that the electrode materials could produce paramagnetic elemental iron particles after the first discharge, but the Fe-selective spectroscopy of the electrode did not return to its original state after charging. They further fitted the spectra and found that the reduced Fe had two different environments: surface iron and agglomerated metal atoms. In addition, FTIR testing of the electrode material before and after cycling confirmed the preservation of oxalate ions. It is worth noting that the oxalate ions may also originate from unreacted ferrous oxalate, and they point out that the absence of gas products can also reflect the retention of oxalate ions, which can lead to overpressure or cell damage.
Subsequently, in 2009, they reported the electrochemical reaction of submicron-sized CoC2O4 materials in the potential range of 0 ~ 3 V under the same electrochemical system[62]. They used XANES (X-ray absorption near edge structure spectroscopy) to observe the formation and incomplete recovery ray absorption near edge structure spectroscopy of elemental Co, which was consistent with the deterioration of crystallinity of cobalt oxalate material observed by electrode XRD after cycling, and EXAFS test showed the formation of fine metal Co particles. In addition, the change of XANES spectra during deep cycling further reveals the reversible transformation between + 2 valence Co and Co simple substance. At the same time, the FTIR data of the electrode after cycling also showed that the oxalate ions were retained, but the detected oxalate ions may come from unreacted cobalt oxalate materials, which made it difficult to judge that the oxalic acid ions existed only in the form of lithium oxalate.
In 2020, our research group used XPS (X-ray photo electron spectroscopy) to analyze the valence state information of Fe element on the surface of the electrode reaction product after the first charge and discharge (as shown in Figure 5C), and found that Fe element showed reversible conversion between + 2 valence and 0 valence during the charge and discharge process, which also confirmed the reversible reduction of + 2 valence iron to elemental iron[36]. Tin oxalate materials are different from them. In the process of electrochemical lithium storage, tin can not only be produced by conversion reaction, but also be alloyed with lithium ions to store lithium. Through ex-situ XRD test and TEM characterization of electrode materials at different potentials, as shown in Fig. 5d, Park et al. revealed that the tin oxalate material can be reversibly converted into metallic tin with low crystallinity during discharge, and the metallic tin generated can undergo reversible alloying reaction with lithium to form Li-Sn alloy at a lower potential[26]. In binary mixed transition metal oxalates, the main reaction mechanism is currently considered to be similar to the conversion reaction mechanism of anhydrous transition metal oxalates, and the theoretical conversion reaction lithium storage mechanism is shown in Formula 2[62⇓⇓~65].
MxM'1-xC2O4 + 2Li+ + 2e- → xM + (1-x)M’ + Li 2C2O4
On the basis of this conversion reaction, Wu et al. Also pointed out in Mn0.33Co0.67C2O4 materials that Li2C2O4 may further react with lithium ions under the catalytic effect of metal nanoparticles[65]. It is worth noting that in addition to the above lithium storage mechanisms, oxalate-based anode materials may also have many complex lithium storage mechanisms, such as capacitive lithium storage caused by fine structure or fine metal particles and reversible decomposition of "organic layer" formed by electrolyte decomposition[32,34].

3.2 New lithium storage mechanism of metal oxalate

3.2.1 Possible sources of additional capacity

In the transition metal oxalate anode materials, the above reaction mechanism cannot fully explain the large additional capacity of the low potential region beyond the conversion reaction type lithium storage mechanism. It was pointed out in earlier studies that this may originate from the reversible decomposition of the polymer gel layer and the capacitive effect[28,31,34][38,39]. Based on the fact that the total charge in a battery consists of a capacitive part and a Faraday part, L LÓpez et al. found that the capacitive effect accounts for a large proportion in both transition metal oxalates containing crystal water and anhydrous transition metal oxalates by using the relationship between current and voltage[28]. However, due to the complex electrochemical process in the low potential region and the difficulty of detecting the intrinsic property changes occurring at the metal-salt interface, the source of the extra capacity has been a controversial topic. Li et al. Used in situ magnetometry to reveal that the main excess capacity in the Fe3O4/Li system comes from the spin-polarized surface capacitance of the metal nanoparticles[66]. During the discharge process, the reduced metal Fe0 can continuously participate in the lithium storage reaction in a low potential region, a large number of spin electrons can be stored in the reduced metal nanoparticles, and additional lithium ions are stored in grain boundaries and crystal planes to form a space charge region. They also point out that the surface capacitance of metal nanoparticles can be extended to transition metal compounds with a wide range of electron density States[64]. The large additional capacity in metal oxalates may also be related to the spin-polarized surface capacitance of metal nanoparticles, but this aspect needs to be further confirmed.

3.2.2 Generation of capacity growth phenomenon

In metallic oxalate-based materials, there is an "unusual" capacity growth behavior in addition to the large amount of extra capacity described above, as shown in fig. 6a[38]. In the process of charge and discharge, the repeated extraction/insertion of lithium ions is easy to force the electrode material to expand in volume and destroy in structure, resulting in the gradual weakening of the capacity of the electrode material in the cycle process. However, at low rates, transition metal oxalate-based materials often exhibit the following regularity: significant capacity fading occurs in the first few cycles, but with further cycling, an "unusual" capacity growth occurs (Figure 6a). The reasons for the capacity growth mentioned in the report can be roughly divided into: (1) morphological structure difference: related to the number of accessible reaction sites and morphological size effect (Fig. 6B, C);(2) The interaction between nano-mixtures: the transformation and activation of transition metal oxalates and nano-mixtures in the process of lithium storage and the interaction between metal nanoparticles and oxalate matrix[35,38][31,34,36][39,60,61]; (3) that change of particle interface and the kinetics of lithium ion migration at the interface[64]; (4) New lithium storage mechanism: interfacial lithium storage and the existence of new lithium storage mechanism[31][30,64]. Considering the reasons analyzed in the current literature, the capacity growth phenomenon is mostly related to the improvement of electrode reaction kinetics during cycling and the new lithium storage mechanism. Although some studies have analyzed the state of batteries under different charge and discharge conditions by means of AC impedance test, and speculated that the capacity growth phenomenon may be related to the stability of the SEI layer during cycling.The physical and chemical properties of the products change before and after the electrochemical reaction, and the complex energy storage characteristics make it difficult to verify the exact relationship between the capacity growth phenomenon and the nano-mixture during the energy storage process[64]. In the future, more characterization methods are needed to explore this "unusual" capacity growth behavior.

3.3 Kinetics of Lithium Storage in Metal Oxalate-based Material

In the process of electrode electrochemical reaction, there are two common kinetic processes: one is the migration of reactant or product atoms in the host crystal lattice and the migration of host atoms in the crystal structure, and the other is the charge transfer caused by oxidation or reduction reaction. Electrode materials are ionic and electronic conductors, and lithium ions in solid electrodes have a variety of migration mechanisms, including interstitial diffusion, grain boundary diffusion and phase boundary diffusion[65]. At the same time, the energy of electron and ion transport is related to atomic defects and morphological defects, and the introduction of appropriate defects can change the lithium ion diffusion barrier, promote the phase transition in the energy storage process, and produce efficient lithium storage kinetic characteristics[66][19].
In 2008, Tirado et al. explored the origin of the large voltage hysteresis in ferrous oxalate materials[46]. Assuming that the Li+/Li is an ideal non-polarized electrode, an equivalent overpotential η = 1/2ΔE (ΔE/mV: the difference between the plateau voltage of the constant-current charge-discharge curve) is approximately obtained. The logarithm of log (rate) was selected to plot ΔE, and it was found that there was a linear relationship between log (rate) and ΔE, which was similar to the Tafel equation, and the Arrhenius behavior was clearly observed. They speculate that the rate of conversion reaction during lithium storage is controlled by the mass transfer between the three solid component product particles produced by electrochemical reaction during charging and discharging. The activation barrier of metathesis reaction is large, if the conversion lithium storage mechanism is regarded as metathesis reaction, the large activation energy in the lithium storage process is not conducive to the improvement of lithium storage capacity of materials[67,68]. Taberna et al. mentioned that the size and properties of the homogeneously dispersed nanocomposites generated in situ after the first charge and discharge may also change the activation energy barrier of the redox reaction[69]. It can be imagined that reasonably controlling the distribution of nano-metal particles that may have catalytic activity after reaction may be an effective way to reduce the potential barrier of conversion reaction, increase the reversibility of electrode reaction and improve the performance of materials. In the process of lithium storage, lithium ions are deintercalated from the crystal lattice of the material, and a smooth and stable ion diffusion channel becomes the key to the reversibility of the metal oxalate-based material during the electrochemical reaction. Our group has established two different 3D lithium ion migration and diffusion pathways in the α and β phases of ferrous oxalate, as shown in Figure 7 a: (1) lithium ions diffuse along the parallel [FeO4])1D channels formed by the FeO6 octahedra in the middle of the four parallel [FeO4] grids[36]; (2) Lithium ions diffuse along the longitudinal channel formed by the breaking of hydrogen bonds and its two sides. Furthermore, based on the Randles-Sevcik equation, it is found that the α@β-FeC2O4 material has the largest lithium ion diffusion coefficient value (fig. 7B). The α@β-FeC2O4 material with both short diffusion path and stable effective channel exhibits a high reversible lithium storage capacity of 1156.27 mAh·g-1 after 500 cycles at a current density of 0.5 C.
Considering that the crystal structure of metal oxalate is approximately unchanged before and after cycling, there is still a lack of research on the migration behavior of lithium ions in the interior and surface of the material. In particular, the diffusion of lithium ions in the large-scale mesoporous structure and the migration path of lithium ions in the process of deintercalation/intercalation are still unclear, and the influence of the morphological structure and crystal structure characteristics of oxalate particles on the migration energy of lithium ions remains to be further studied.

3.4 Modification Strategies of Metal Oxalate-based Material

Metal oxalate-based anode materials have attracted the attention of many researchers because of their high energy density and excellent rate performance in lithium-ion batteries. An ideal anode material for lithium-ion batteries should possess high initial coulombic efficiency and high reversible capacity retention. However, in the battery system, it was found that the irreversible reaction of the organic solvent in the electrolyte and the destruction of the crystal structure of the metal oxalate during the first discharge process resulted in low coulombic efficiency and poor capacity retention of the metal oxalate-based materials during the first cycle. In addition, the poor electronic conductivity of metal oxalate-based materials is not conducive to the rate performance. In order to solve the above defects and obtain excellent electrochemical performance, the following modification strategies are often used: material morphology crystal control, particle interface carbon composite modification and metal element doping.

3.4.1 Control of material morphology and crystal form

Mesoporous materials have lower activation energy than solid materials[17]. Oxalate materials with specific crystal forms, unique morphologies and porous characteristics and nano-size can provide different active site densities, ion migration channels and low conversion reaction barriers for lithium ion storage[36]. Table 1 compares the performance differences of metal oxalate-based lithium-ion battery anode materials with different morphologies. It can be seen that the electrochemical properties of metal oxalate-based materials with different morphologies are quite different, and the morphology control is an effective method to improve the electrochemical properties of metal oxalate-based materials. Compared with the nanoribbons of ferrous oxalate obtained by reverse micelle method, the rod-like ferrous oxalate with high specific surface area, cocoon-like and 1D multilayer mesoporous structure can significantly improve the cycle stability and rate capability of ferrous oxalic acid anode material by virtue of its unique structural advantages[46][35][38]. Constructing a stable active material stacking environment is also an idea to alleviate the volume change of materials before and after lithium storage.
Based on the self-etching method, the 1D ferrous oxalate nanotube array was obtained by Zhong of Zhejiang University, which was directly connected to the current collector. The stable gap between the nanotube array and the smooth 1D conductive channel made the material show excellent lithium storage performance[34]. The volume of materials will inevitably change in the process of deionization/intercalation, and it is very important to prepare electrode materials with stable crystal structure and small particle size to alleviate the volume change of materials and improve the rate performance of materials. As far as the synthesis of ferrous oxalate by the solvothermal method is concerned, compared with metastable β-FeC2O4,After thermal conversion, the atomic gaps in the crystal structure of the steady-state α-FeC2O4 are larger, and the size of the material particles is also larger, that is to say, in the process of controlling the shape of the metal oxalate-based material, the relationship between the crystal form and the size of the material can be properly regulated and controlled to obtain the metal oxalate-based material with similar experimental conditions and more excellent lithium storage kinetic conditions[36]. Although controlling the crystal morphology of materials is an effective way to improve the electrochemical performance of metal oxalate-based materials, there is still no suitable crystal morphology control to solve all the problems of metal oxalate-based materials in the process of energy storage.

3.4.2 Particle interface carbon composite modified

The change of the microscopic morphology characteristics of the oxalate particles can provide different lithium ion diffusion paths and active sites for the storage of Li+. The mixture of oxalate particles with certain morphology characteristics and conductive carbon black can provide a specific interface and ion transmission channel for electron and lithium ion transmission. Most metal oxalate-based materials generate lithium oxalate Li2C2O4 in the process of lithium storage, and lithium oxalate is often regarded as an insulator, which is not conducive to the performance of materials.The recombination of conductive phases such as carbon at the interface of materials can not only promote the electron transfer between metal oxalate-based material particles, but also compensate the charge transfer between reaction products and increase the reversibility of electrode reaction. However, transition metal oxalate-based materials have poor thermal stability, and it is difficult to coat carbon materials on the interface of metal oxalate-based materials by high temperature sintering method[28]. Low-temperature electrostatic self-assembly, low-temperature porous carbon encapsulation and other methods can combine different dimensions of highly conductive carbon skeletons with oxalate, thus obtaining composites with excellent performance[69]. In our research group, Fe2/3Cu1/3C2O4·xH2O/MWCNTs composites were prepared by electrostatic self-assembly technology and solvothermal method to realize the double composite of copper oxalate, carbon nanotubes and ferrous oxalate[61]. The 1D carbon nanotubes with high electrical conductivity and high mechanical strength grow inside the particles and around the material to construct the 3D spatial carbon skeleton structure, form the uniform conductive network path and maintain the stability of the Li+ diffusion channel between the particles. By virtue of its unique structural advantages and the synergistic effect between MWCNTs and hydrated copper oxalate, the material shows high lithium storage performance. After 100 cycles at a current density of 0.5 A/G, its reversible discharge specific capacity is still as high as 530 mAh·g-1. Feng et al. prepared Cu1/3Co2/3C2O4·xH2O/FGO materials by co-precipitation method. The 2D sheet-like FGO (functional graphene oxide) provided a fast Li+ diffusion channel for the material, but also hindered the aggregation of active material particles distributed on the surface of FGO, which increased the contact area between the active material and the electrolyte[72]. The unique design allows the material to exhibit excellent energy storage capability, with a reversible capacity of 1134.9 mAh·g-1 after 200 cycles at a current density of 1 A/G. Deng et al. prepared the 3DFC@CuC2O4·xH2O anode material by embedding CuC2O4·xH2O nanocrystals into 3D fungal structured carbon. The layered porous carbon provided an ideal structure for rapid electron and ion transfer and reduction of the hydrated copper oxalate material, enabling the material to exhibit outstanding rate capability and cycle stability[73].
Although the combination of the advantages of micro-nano structure regulation and different dimensions of conductive carbon materials can significantly improve the performance of materials, the repeated structural reorganization of conversion materials during charging and discharging can easily lead to the partial shedding of active particles and make it difficult to maintain the original unique morphological and structural characteristics. It is also a strategy to improve the electrochemical performance of metal oxalate-based materials by using the shell structure to protect the internal electrode active materials, limit the occurrence of side reactions and avoid the dissolution of lithium oxalate[34,58]. In this regard, our group used electrostatic self-assembly technology and in-situ thermal decomposition to synthesize Fe2O3 nanodot-coated multilayer ferrous oxalate material FeC2O4@Fe2O3/rGO,Fe2O3 nanodot-shell layer to promote the formation of stable SEI layer and uniform compact amorphous organic layer during cycling, and the unique core-shell structure protects FeC2O4 particles from damage during cycling[74]. The material exhibited a high reversible capacity of 922 mAh·g-1 after 500 cycles at a rate of 0.5 A/G.

3.4.3 Metal element doping

Cobalt oxalate has excellent electrochemical performance, but the toxicity, high price and environmental problems of cobalt limit its application. It is also a desirable strategy to use Fe and Mn elements with similar electrochemical performance, low cost and low toxicity to partially replace Co, and to improve the electrochemical performance of cobalt oxalate through the synergistic effect of various oxalates and the catalytic effect of nano-transition metal elements. In the early stage, Tirado et al. doped Fe and Mn transition metal elements into cobalt oxalate lattice by reverse micelle method to form Fe-Co and Co-Mn solid solution nanoribbons with Co element partially replaced[63,64]. It was found that the partial substitution of Fe was helpful to improve the cycle stability of cobalt oxalate, and showed the synergistic effect of cobalt oxalate and ferrous oxalate in performance, while the partial substitution of Mn did not improve the electrochemical performance of ferrous oxalate and cobalt oxaliate. However, the difference is that Wu et al. prepared Mn0.33Co0.67C2O4 with layered urchin-like microspheres by chemical co-precipitation method, which showed 924 mAh·g-1 reversible capacity in the second cycle at a current density of 0.5 A/G, and the reversible capacity could still be maintained at about 800 mAh·g-1 after 300 cycles[65]. Compared with the previous nanoribbon manganese-cobalt metal oxalate, the Mn doping in the Mn-doped layered urchin-like manganese-cobalt oxalate microspheres significantly improves the cycle stability of the cobalt oxalate anode material. It can be seen that the electrochemical performance of metal oxalate-based anode materials has a strong dependence on the morphology. Similarly, Ang et al. Synthesized rod-like mixed metal oxalate solid solution MxC2O4(M=Mn,Co 0≤x≤1) doped with manganese element by one-step solvothermal method[47]. It was found that the cobalt-manganese oxalate solid solution showed excellent electrochemical performance when the Mn doping amount was 0. 48, and there was a positive synergistic effect between the cobalt-manganese oxalate solid solution. It exhibits a 1389 mAh·g-1 initial discharge capacity at 1 C and a high reversible capacity of 1000 mAh·g-1 after 100 cycles, and its capacity retention rate is much higher than that of cobalt oxalate materials at the same rate.
In many studies, morphology control and particle interface carbon material composite are still the main methods to improve the electrochemical performance of metal oxalate anode materials. According to the above strategy, the electrochemical performance of metal oxalate-based materials has been significantly improved, and some of the metal oxalate-based materials have reversible capacity exceeding the 1000 mAh·g-1 and show capacity retention of ~ 80%. Although there are many deficiencies in the application of metal oxalate-based anode materials in lithium-ion batteries, it is still expected that metal oxalate-based materials with different morphologies and structures can be synthesized to achieve better lithium storage capacity by using structural effects.

4 Applications in Other Ion Batteries

Lithium, sodium, and potassium metals have similar chemical characteristics, and all three alkali metal ions can react with intercalation, conversion, and alloying anode materials for energy storage[75,76]. In recent years, considering the excellent energy storage capacity of metal oxalate-based materials in the process of lithium storage, the materials have also been explored as anode materials for sodium and potassium ion batteries.

4.1 Sodium-ion battery

Similar to lithium-ion batteries, sodium-ion batteries can store Na+ through insertion, alloying and conversion energy storage mechanisms. However, the relatively large ionic radius of sodium ions slows down the rate of extraction of sodium ions from materials[75,76]. Typical intercalation materials, such as hard carbon, have both stable cycle performance and long cycle life. However, the inherent disorder of hard carbon tends to hinder the diffusion of sodium ions at high rates[77]. The alloyed composite has the advantage of high capacity, but the significant volume change during charge and discharge is easy to produce large capacity loss[78]. For these reasons, a large number of research focuses have been transferred to conversion materials such as metal oxides and fluorides. Although these materials have higher capacity for multi-electron transfer in the process of sodium storage, the Na2O and NaF produced after the conversion reaction are not active and are electronic insulators, which are not conducive to electron transfer in the process of cycling[79,80]. For the novel conversion-type metal oxalate anode material, the wide valence change of transition metal elements makes it easier to achieve high energy density, and the NaC2O4 generated after the conversion reaction has stronger activity than Na2O and NaF materials, which is more conducive to the reversible storage of Na+[62].
In 2017, Park et al. Synthesized SnC2O4/rGO composites through layer-by-layer self-assembly technology[26]. Through the galvanostatic charge-discharge test, it is found that the material shows 170 mAh·g-1 reversible capacity in the first discharge process. In 2018, Jo et al. First reported the sodium storage capacity and new sodium storage mechanism of cobalt oxalate through similar structural and morphological control strategies (Figure 8a C-NaCrO2//C-CoC2O4 full battery schematic)[53]. They observed the XRD phase evolution information of carbon-coated C-CoC2O4 electrode materials in the electrolyte of propylene carbonate-fluoroethylene carbonate dissolved with NaPF6 under different charge-discharge conditions, and found the diffraction peaks of NaC2O4, CoC2O4 and Co, respectively.At the same time, the electron diffraction patterns of these three substances were also observed by TEM selected area electron diffraction, which preliminarily indicated that the conversion type sodium storage mechanism accompanied by the reversible conversion of the valence state of cobalt element produced by sodium oxalate. It is worth noting that after 200 cycles, the electrode detected the diffraction peak of cobalt oxalate, and also observed the diffraction peak of NaOH, which may be caused by water contamination during the test. In addition, Raman and ToF-SIMS further confirmed the formation of sodium oxalate and the recovery of cobalt oxalate. Because the Na2CO3 was unstable at low voltage, the ToF-SIMS test observed the appearance and gradual enhancement of the signal of NaCl O 3 + fragment below 0. 6 V, implying the existence of Na — C — O chemical bond, which also indicated the formation of sodium oxalate, consistent with the results of sodium oxalic acid formation shown in Raman spectra. After mixing cobalt oxalate with acetylene, the C-CoC2O4 material still had a reversible capacity of 247.5 mAh·g-1 after 200 cycles at a current density of 0.2 C (60 mA/G) (Figure 8 C). In addition, the application of the material to a full battery also demonstrated a high reversible capacity (Fig. 8B). Zhang et al. prepared CoC2O4·2H2O/rGO materials using a multi-step solvent/hydrothermal strategy[60]. The presence of rGO not only suppresses the volume change of the material during energy storage, but also accelerates the electron and ion transfer in the material. The material exhibits excellent reversibility and cycling stability, and the reversible capacity is still as high as 221.1 mAh·g-1 after 100 cycles at a current density of 0.2 A/G.

4.2 Potassium-ion battery

Although conversion-type anode materials are widely used in lithium and sodium secondary batteries due to their large reversible capacity, reports on their application in potassium-ion batteries are limited. For potassium-ion batteries, it is still a challenge to find suitable electrode materials to accommodate potassium ions. So far, only a few materials, such as intercalation materials doped with graphene, alloy reaction mechanism materials and conversion metal oxide anode materials, have been used in potassium-ion batteries[81⇓⇓⇓~85]. It is urgent to explore new anode materials with suitable K+ deintercalation/intercalation for potassium-ion batteries.
In 2019, Wang et al. Combined the unique 1D porous cobalt oxalate with 2D sheet graphene, and successfully prepared CoC2O4/GO composites[86]. The unique structural advantages of the material provide more adsorption sites and shorter paths for the storage and transport of potassium ions, and also alleviate the volume effect of the material. The material remained 166 mAh·g-1 after 50 cycles at a current density of 0.05 mA/G. In 2020, Jo et al. mixed the CoCl2·2H2O dispersion containing CNTs (carbon nanotubes) with the NaC2O4 solution to prepare the CoC2O4/CNTs material, as shown in Fig. 9 a, B)[87]. In the potential range of 0 ~ 3 V, they found that the traditional conversion lithium storage mechanism was also applicable to cobalt oxalate anode materials for potassium ion batteries in propylene carbonate-fluoroethylene carbonate electrolyte with dissolved KPF6. They carried out in-situ XRD tests and TEM selective domain electron diffraction tests on CoC2O4/CNTs electrodes under different charge-discharge conditions to illustrate the reversible conversion mechanism between divalent Co and elemental Co produced by lithium oxalate during the first cycle of the material. It is worth noting that the cobalt oxalate material with weaker XRD diffraction intensity can still be found after the same test of the electrode after 200 cycles. At the same time, the XANES detection of the electrode material after cycling again confirmed that the divalent cobalt element was reduced to produce elemental Co, and the ToF-SIMS test also found the existence of K2CO+ fragments derived from the K — C — O bond, which again verified the production of lithium oxalate in the XRD results. The reversible capacity of the CoC2O4/CNTs material is still as high as 288 mAh·g-1 after 200 cycles at a rate of 0.2 C, and the capacity retention is higher than 73%. Although the conversion reaction produced repeated structural reorganization during cycling, the CoC2O4 with low crystallinity remained attached to the CNTs (Fig. 9 C, d). The unique structural advantages and the high conductivity of CNTs make the composites show excellent potassium storage capacity. The excellent electrochemical performance of metal oxalate-based materials in lithium, sodium and potassium ion batteries, coupled with the advantages of low cost, green environmental protection and small volume change in the process of energy storage, make metal oxalate-based materials a potential competitor in the field of energy storage. However, the capacity of oxalate-based anode materials in sodium/potassium ion batteries is significantly lower than that in lithium ion batteries, which is mainly due to the following reasons: (1) the radius of sodium/potassium ions is larger.It is more difficult to migrate inside the material, so the conversion reaction will be more incomplete in the process of charging and discharging, resulting in some oxalate not reacting or reacting oxalate not reversibly converting; (2) The special mesoporous structure of transition metal oxalate materials is easy to cause interfacial lithium storage and capacitance effect, but this phenomenon has not been found in sodium/potassium ion batteries; (3) The occurrence of other irreversible side reactions also easily leads to poor sodium and potassium storage capacity, such as the formation of K-based SEI layer by irreversible decomposition of electrolyte[87].

5 Conclusion and prospect

In this paper, the crystal structure of metal oxalate-based anode materials was introduced, the diversified energy storage mechanism and the kinetic characteristics of the energy storage process were discussed, and the research progress of the materials in metal ion batteries was reviewed. Although strategies such as crystal morphology design and particle-interface carbon material composite can significantly improve the electrochemical performance of the materials, the poor capacity retention rate of metal oxalate materials and the obvious capacity loss in the early cycle still exist. Further improvement of the electrochemical performance of metal oxalate-based anode materials still faces the following challenges: (1) Although the conversion reaction mechanism in some metal oxalate-based materials has been gradually confirmed, the specific lithium storage pathway, the source of a large number of additional capacity in the lithium storage process and the reasons for the "unusual" capacity growth phenomenon are still unclear; (2) the specific role of the material with various nanoblends during electrochemical energy storage remains unexplained; (3) The effect of crystal water on the electrochemical properties of the materials remains to be verified.
Based on the above analysis, we believe that the future metal oxalate-based materials as anode materials for high energy density metal ion batteries can make further breakthroughs in the following aspects: (1) energy storage mechanism, which requires a deeper understanding of the diversified energy storage mechanism of metal oxalate-based materials; (2) crystal form morphology control, wherein that crystal form control optimize a metal ion diffusion channel in a metal oxalate microstructure, and the nanoscale morphology control increases the density of reaction site and shortens a chemical diffusion path during electrochemical energy storage; (3) that catalytic activity is regulate and controlled, the potential catalytic effect of the metal particle is fully utilized, the activation energy of the electrochemical conversion reaction is reduced, and the reversibility of the electrode reaction is increased so as to improve the electrochemical performance of the material; (4) that carbon substance at the interface of the material is compound, and the low-temperature carbon substance is coated to further optimize the conductivity of the material and improve the electrochemical performance of the material; And (5) a plurality of energy storage material are co-compounded with oxalate, and that electrochemical performance of the metal oxalate-based material is improved by utilize the energy storage advantages of different materials.
At present, metal oxalate-based materials show high energy storage capacity, excellent rate and cycle characteristics in lithium, sodium and potassium alkali metal ion batteries by virtue of their diversified energy storage mechanisms. It is believed that in the future, relying on the new material characterization technology and the continuous development of science and technology, the energy storage mechanism and dynamic characteristics of metal oxalate-based anode materials will be continuously clarified, and the materials will play a greater role in the field of green energy storage.

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]

Xu C F, Fang X, Zhan J, Chen J X, Liang F. Prog. Chem., 2020, 32(6): 836.
[2]

( 徐昌藩, 房鑫, 湛菁, 陈佳希, 梁风. 化学进展, 2020, 32(6): 836.)
[3]

Li H, Wu C, Wu F, Bai Y, Acta Chimica Sinica, 2014, 72(01):21.
[4]

( 李慧, 吴川, 吴锋, 白莹. 化学学报, 2014, 72(01):21.)
[5]

Liang S Z, Cheng Y J, Zhu J, Xia Y G, Müller-Buschbaum P. Small Methods, 2020, 4(8): 2000218.
[6]

Liang Y R, Zhao C Z, Yuan H, Chen Y, Zhang W C, Huang J Q, Yu D S, Liu Y L, Titirici M M, Chueh Y L, Yu H J, Zhang Q. InfoMat, 2019, 1(1): 6.
[7]

Fan E S, Li L, Wang Z P, Lin J, Huang Y X, Yao Y, Chen R J, Wu F. Chem. Rev., 2020, 120(14): 7020.
[8]

Wang Y Q, Gu L, Guo Y G, Li H, He X Q, Tsukimoto S, Ikuhara Y, Wan L J. J. Am. Chem. Soc., 2012, 134(18): 7874.
[9]

Ren H, Yu R B, Wang J Y, Jin Q, Yang M, Mao D, Kisailus D, Zhao H J, Wang D. Nano Lett., 2014, 14(11): 6679.
[10]

Wang J, Zhou Y K, Hu Y Y, O’Hayre R, Shao Z P. J. Phys. Chem. C, 2011, 115(5): 2529.
[11]

Jin H C, Xin S, Chuang C H, Li W D, Wang H Y, Zhu J, Xie H Y, Zhang T M, Wan Y Y, Qi Z K, Yan W S, Lu Y R, Chan T S, Wu X J, Goodenough J B, Ji H X, Duan X F. Science, 2020, 370(6513): 192.
[12]

Li C L, Liu C, Wang W, Mutlu Z, Bell J, Ahmed K, Ye R, Ozkan M, Ozkan C S. Sci. Rep., 2017, 7(1): 1.
[13]

Zuo X X, Zhu J, Müller-Buschbaum P, Cheng Y J. Nano Energy, 2017, 31: 113.
[14]

Yin X M, Li C C, Zhang M, Hao Q Y, Liu S, Chen L B, Wang T H. J. Phys. Chem. C, 2010, 114(17): 8084.
[15]

Usui H, Kono T, Sakaguchi H. International Journal of Electrochemical ence, 2012, 7(5):4322.
[16]

Bresser D, Mueller F, Fiedler M, Krueger S, Kloepsch R, Baither D, Winter M, Paillard E, Passerini S. Chem. Mater., 2013, 25(24): 4977.
[17]

Kim M C, Kim S J, Han S B, Kwak D H, Hwang E T, Kim D M, Lee G H, Choe H S, Park K W. J. Mater. Chem. A, 2015, 3(45): 23003.
[18]

Bell J, Ye R, Ahmed K, Liu C, Ozkan M, Ozkan C S. Nano Energy, 2015, 18: 47.
[19]

Liu H, Wang G X, Liu J, Qiao S Z, Ahn H. J. Mater. Chem., 2011, 21(9): 3046.
[20]

Cao K Z, Jiao L F, Liu Y C, Liu H Q, Wang Y J, Yuan H T. Adv. Funct. Mater., 2015, 25(7): 1082.
[21]

Ma Y, Liu P, Xie Q, Zhang C, Wang L, Peng D. Materials today energy (Materials Today Energy), 2020, 16:100383.
[22]

Fu C P, Mahadevegowda A, Grant P S. J. Mater. Chem. A, 2016, 4(7): 2597.
[23]

Gao J, Lowe M A, Abruña H D. Chem. Mater., 2011, 23(13): 3223.
[24]

Wang L B, Tang W J, Jing Y, Su L W, Zhou Z. ACS Appl. Mater. Interfaces, 2014, 6(15): 12346.
[25]

Zhong Y R, Su L W, Yang M, Wei J P, Zhou Z. ACS Appl. Mater. Interfaces, 2013, 5(21): 11212.
[26]

Zhao S Q, Yu Y, Wei S S, Wang Y X, Zhao C H, Liu R, Shen Q. J. Power Sources, 2014, 253: 251.
[27]

Zhou L K, Kong X H, Gao M, Lian F, Li B J, Zhou Z F, Cao H Q. Inorg. Chem., 2014, 53(17): 9228.
[28]

Park J S, Jo J H, Yashiro H, Kim S S, Kim S J, Sun Y K, Myung S T. ACS Appl. Mater. Interfaces, 2017, 9(31): 25941.
[29]

Shi S, Hua X, Guo H. Ceramics International (Ceramics International), 2018, 44(12):13495.
[30]

LÓpez M C, Tirado J L, PÉrez Vicente C. J. Power Sources, 2013, 227: 65.
[31]

Qi Z Q, Wu Y D, Li X F, Qu Y, Yang Y Y, Mei D J. Ionics, 2020, 26(1): 33.
[32]

Kang W P, Shen Q. J. Power Sources, 2013, 238: 203.
[33]

Zhang Y H, Lu Z X, Guo M Q, Bai Z C, Tang B. JOM, 2016, 68(11): 2952.
[34]

Ang W A, Cheah Y L, Wong C L, Prasanth R, Hng H H, Madhavi S. J. Phys. Chem. C, 2013, 117(32): 16316.
[35]

Xu J M, He L, Liu H, Han T, Wang Y J, Zhang C J, Zhang Y H. Electrochimica Acta, 2015, 170: 85.
[36]

Zhong Y. Doctoral Dissertation of Zhejiang University, 2016.
[37]

( 钟媛. 浙江大学博士论文, 2016.).
[38]

Ang W A, Gupta N, Prasanth R, Madhavi S. ACS Appl. Mater. Interfaces, 2012, 4(12): 7011.
[39]

Zhang K Y, Li Y, Wang Y K, Zhao J Y, Chen X M, Dai Y N, Yao Y C. Chem. Eng. J., 2020, 384: 123281.
[40]

Zhang K Y, Li Y, Hu X J, Liang F, Wang L, Xu R H, Dai Y N, Yao Y C. Chem. Eng. J., 2021, 404: 126464.
[41]

Zhang K Y, Liang F, Wang Y K, Dai Y N, Yao Y C. J. Alloys Compd., 2019, 779: 91.
[42]

Yang Y, He L, Lu J F, Liu Z Y, Wang N Y, Su J, Long Y F, Lv X, Wen Y X. Electrochimica Acta, 2019, 321: 134673.
[43]

Kim H, Choi W I, Jang Y, Balasubramanian M, Lee W, Park G O, Park S B, Yoo J, Hong J S, Choi Y S, Lee H S, Bae I T, Kim J M, Yoon W S. ACS Nano, 2018, 12(3): 2909.
[44]

Huang X L, Chai J, Jiang T, Wei Y J, Chen G, Liu W Q, Han D X, Niu L, Wang L M, Zhang X B. J. Mater. Chem., 2012, 22(8): 3404.
[45]

Pramanik A, Maiti S P, Mahanty S. Sciense Letters, 2015, 4:104.
[46]

Li B J, Cao H Q, Shao J, Zheng H, Lu Y X, Yin J F, Qu M Z. Chem. Commun., 2011, 47(11): 3159.
[47]

Inamdar A I, Chavan H S, Aqueel Ahmed A T, Jo Y, Cho S, Kim J, Pawar S M, Kim H, Im H. J. Alloys Compd., 2020, 829: 154593.
[48]

Pramanik A, Maiti S, Mahanty S. J. Mater. Chem. A, 2014, 2(43): 18515.
[49]

AragÓn M J, LeÓn B, PÉrez Vicente C, Tirado J L. Inorg. Chem., 2008, 47(22): 10366.
[50]

Ang W A E, Cheah Y L, Wong C L, Hng H H, Madhavi S. J. Alloys Compd., 2015, 638: 324.
[51]

Baran E J, Monje P V. Met. Ions Life Sci. 2008, 8: 219.
[52]

Baran E J. J. Coord. Chem., 2014, 67(23/24): 3734.
[53]

Krishnamurty K V, Harris G M. Chem. Rev., 1961, 61(3): 213.
[54]

Lenchev A, Trifonova E P. Cryst. Res. Technol., 1990, 25(9): 1017.
[55]

Molinier M, Price D J, Wood P T, Powell A K. J. Chem. Soc., Dalton Trans., 1997(21): 4061.
[56]

Jo C H, Yashiro H, Yuan S, Shi L Y, Myung S T. ACS Appl. Mater. Interfaces, 2018, 10(47): 40523.
[57]

Barazorda-Ccahuana H L, Nedyalkova M, Kichev I, Madurga S, Donkova B, Simeonov V. ACS Omega, 2020, 5(16): 9071.
[58]

Su Y Z, Chen H Y, Hu Z X, Liu S N, Xiao L H, Jiang M. Journal of Central South University(Science and Technology), 2013, 44(06):2237.
[59]

( 苏玉长, 陈宏艳, 胡泽星, 刘赛男, 肖立华, 江敏. 中南大学学报(自然科学版), 2013, 44(06):2237.)
[60]

Nie L C. Master's Dissertation of Zhejiang University, 2014.
[61]

( 聂林才. 上海大学硕士论文, 2014.).
[62]

Zhang K Y, Xu R H, Wei R H, Li Y, Wang Y K, Zhang Y N, Dai Y N, Yao Y C. Mater. Chem. Phys., 2020, 243: 122676.
[63]

Yeoh J S, Armer C F, Lowe A. Mater. Today Energy, 2018, 9: 198.
[64]

Oh H J, Jo C H, Yoon C S, Yashiro H, Sun J K, Passerini S, Sun YK, Myung S T. NPG Asia materials. 2016, 8(5):270.
[65]

Zhang Y, Wang C, Dong Y, Wei R, Zhang J. Chem.-A Eur. J., 2021, 27(3):993.
[66]

Zhang K Y, Gao G, Li Y, Wang Y K, Xu R H, Dai Y N, Yao Y C. Mater. Lett., 2020, 266: 127476.
[67]

AragÓn M J, LeÓn B, PÉrez Vicente C, Tirado J L, Chadwick A V, Berko A, Beh S Y. Chem. Mater., 2009, 21(9): 1834.
[68]

LeÓn B, Vicente C P, Tirado J L. Solid State Ion., 2012, 225: 518.
[69]

AragÓn M J, LeÓn B, Serrano T, PÉrez Vicente C, Tirado J L. J. Mater. Chem., 2011, 21(27): 10102.
[70]

Wu X H, Guo J H, McDonald M J, Li S G, Xu B B, Yang Y. Electrochimica Acta, 2015, 163: 93.
[71]

Li Q, Li H S, Xia Q T, Hu Z Q, Zhu Y, Yan S S, Ge C, Zhang Q H, Wang X X, Shang X T, Fan S T, Long Y Z, Gu L, Miao G X, Yu G H, Moodera J S. Nat. Mater., 2021, 20(1): 76.
[72]

Yu L P, Zhou X H, Lu L, Wu X L, Wang F J. ChemSusChem, 2020, 13(20): 5361.
[73]

Lu X X, Mao Q N, Chen Y F, Bao L, Tong L C, Xiong Q Q, Qin H Y, Pan H G, Ji Z G. Electrochimica Acta, 2018, 282: 351.
[74]

Taberna P L, Mitra S, Poizot P, Simon P, Tarascon J M. Nat. Mater., 2006, 5(7): 567.
[75]

Pang H, Wang S, Li X, Zhao S, Li S. International Journal of Electrochemical Science, 2013, 8(3):4174.
[76]

Hu Y N, Lin Z H, Min F X, Teng F, Wu H M, Wang S Q, Liu J W, Feng C Q. J. Nanosci. Nanotechnol., 2020, 20(3): 1740.
[77]

Feng F, Kang W P, Yu F Q, Zhang H, Shen Q. J. Power Sources, 2015, 282: 109.
[78]

Deng J T, Wang L, Deng J, Fang Y, Lin Y, Hu Y H. J. Mater. Chem. A, 2020, 8(6): 3397.
[79]

Zhang K Y, Zhang D, Li Y, Wang L, Liang F, Dai Y N, Yao Y C. Appl. Surf. Sci., 2020, 507: 145051.
[80]

Li L, Zheng Y, Zhang S L, Yang J P, Shao Z P, Guo Z P. Energy Environ. Sci., 2018, 11(9): 2310.
[81]

Wu X Y, Leonard D P, Ji X L. Chem. Mater., 2017, 29(12): 5031.
[82]

Irisarri E, Ponrouch A, Palacin M R. J. Electrochem. Soc., 2015, 162(14): A2476.
[83]

Ramireddy T, Sharma N, Xing T, Chen Y, Leforestier J, Glushenkov A M. ACS Appl. Mater. Interfaces, 2016, 8(44): 30152.
[84]

Li C L, Chen K Y, Zhou X J, Maier J. Npj Comput. Mater., 2018, 4(1): 1.
[85]

Lu Y C, Ma C Z, Alvarado J, Kidera T, Dimov N, Meng Y S, Okada S. J. Power Sources, 2015, 284: 287.
[86]

Vaalma C, Buchholz D, Passerini S. Curr. Opin. Electrochem., 2018, 9: 41.
[87]

Hosaka T, Kubota K, Hameed A S, Komaba S. Chem. Rev., 2020, 120(14): 6358.
[88]

Ju Z C, Li P Z, Ma G Y, Xing Z, Zhuang Q C, Qian Y T. Energy Storage Mater., 2018, 11: 38.
[89]

Chen Z, Yin D G, Zhang M. Small, 2018, 14(17): 1703818.
[90]

Li D P, Zhu M, Chen L N, Chen L, Zhai W, Ai Q, Hou G M, Sun Q, Liu Y, Liang Z, Guo S R, Lou J, Si P C, Feng J K, Zhang L, Ci L J. Adv. Mater. Interfaces, 2018, 5(15): 1800606.
[91]

Wang L F, Wei K Y, Zhang P J, Wang H, Qi X J, Wu X, Zhao W, Ju Z C. J. Nanosci. Nanotechnol., 2019, 19(6): 3610.
[92]

Jo C H, Jo J H, Choi J U, Yashiro H, Kim H, Myung S T. ACS Sustainable Chem. Eng., 2020, 8(9): 3743.

Funding

National Natural Science Foundation of China(52064031)

National Natural Science Foundation of China(52104302)

Natural Science Foundation of Yunnan Province(2018HB012)

Natural Science Foundation of Yunnan Province(202101BZ070001-020)

Xingdian Talent Support Project(KKS9202052010)

PDF (10408KB)

2401

Accesses

0

Citation

Detail
Sections
Recommended

/

〈 〉

Address of Editorial Office: No. 33 Beisihuan Xilu, Zhongguancun , Beijing 100190, China
Tel: +86 10 8262 7757
Fax: +86 10 8262 7757
E-mail: progchem@mail.las.ac.cn
http://www.progchem.ac.cn
    • 　
    Copyright © Editorial Office of Progress in Chemistry