CN112563585B - Electrolyte for alkali metal battery and preparation and application thereof - Google Patents

Electrolyte for alkali metal battery and preparation and application thereof Download PDF

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CN112563585B
CN112563585B CN201910851959.9A CN201910851959A CN112563585B CN 112563585 B CN112563585 B CN 112563585B CN 201910851959 A CN201910851959 A CN 201910851959A CN 112563585 B CN112563585 B CN 112563585B
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electrolyte
lithium
alkali metal
additive
battery
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CN112563585A (en
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张洪章
李先锋
罗洋
张华民
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to an electrolyte additive for an alkali metal battery, and preparation and application thereof. By adding the organic polymer nitro compound into the electrolyte, the nitro compound is used as a reactant to participate in the generation of an electrode/electrolyte interface film, the continuous reaction and consumption of the electrolyte and alkali metal are effectively inhibited, the nitro functional group on the polymer nitrate with improved battery circulation stability can be reduced in situ on the metal surface, the generated product has high ionic conductivity, the interface ion transmission is greatly accelerated, and the ion deposition uniformity is improved. Meanwhile, the polymer skeleton can react in situ to generate an organic matter compact film which covers the surface of lithium, and the organic matter compact film has good flexibility and viscosity and can effectively relieve the inorganic layer fracture caused by volume expansion of the negative electrode, thereby inhibiting dendritic crystal growth.

Description

Electrolyte for alkali metal battery and preparation and application thereof
Technical Field
The invention relates to an electrolyte additive for an alkali metal battery, and preparation and application thereof.
Background
Currently, the world market for electric vehicles and portable electronic devices, including passenger cars, buses, and passenger cars, is rapidly growing. Lithium ion batteries having high charge and discharge voltages and long cycle lives are widely used as power sources for portable electronic devices and electric automobiles, but due to the limitation of theoretical energy density thereof, development of novel electrode materials having higher energy density is required. Wherein the alkali metal material, especially lithium metal material, has high theoretical energy density (3860mAh g) as the negative electrode material -1 ) And the advantage of a low electrochemical potential (-3.040V vs. she), have received a great deal of attention from researchers in recent years.
However, two problems still remain to be solved in the application of the alkali metal cathode. One is the dendrite problem. Due to the non-uniformity of the alkali metal ion deposition, moss/dendrites are formed in the charge-discharge cycle process, and the moss/dendrites easily pierce through the diaphragm to cause short circuit in the battery and even cause fire. Another problem is instability of the electrode/electrolyte interface. The alkali metal reacts spontaneously with the electrolyte to form a solid electrolyte interface film (SEI), which is continuously damaged and repaired along with the volume expansion of the negative electrode during charge and discharge cycles, resulting in the continuous consumption of the alkali metal and the electrolyte, and the reduction of the coulombic efficiency and cycle life of the alkali metal battery.
Lithium metal is currently the most widely studied alkali metal electrode material, but its practical application is limited by dendrite and interfacial instability. At present, relevant solutions have been proposed, and a solid electrolyte can be adopted to inhibit the growth of dendrites by designing a 3D framework structure, but some problems still exist and need to be solved urgently. The 3D skeleton structure can slow down dendrite growth by reducing current density, but cannot isolate lithium metal from directly contacting an electrolyte to inhibit the occurrence of side reactions; while the inorganic solid-state electrolysis has high mechanical strength, the interface resistance is large, and the contact with lithium metal is poor; although the polymer electrolyte has good flexibility and elasticity, the room-temperature ionic conductivity is relatively low (<10 -4 S cm -1 ). By designing effective electrolyte, a stable SEI film is formed in situ to improve the uniformity and stability of an interface, which is an important strategy for effectively inhibiting the growth of lithium dendrites and improving the cycling stability and safety performance of a lithium cathode.
Lithium nitrate is a common additive in ether electrolyte of a lithium metal battery and can induce lithium ions to form uniform spherical deposition; the lithium nitride generated after in-situ reduction is a fast ion conductor, so that the transmission of interface lithium ions is accelerated, the deposition uniformity of lithium is improved, and the growth of dendritic crystals is delayed. However, lithium nitrate is difficult to dissolve in ester solvents and cannot be used in commercial lithium ion batteries; the generated lithium nitride is high in rigidity and is easy to crack and fall off along with the volume expansion of the negative electrode, so that new metal lithium is exposed, and the lithium nitrate is continuously consumed, and therefore an organic electrolyte additive for the alkali metal battery is found, the organic electrolyte additive has high solubility, and the generated SEI film has good flexibility and mechanical stability, so that the universality and the cycling stability of the organic electrolyte additive in the alkali metal battery can be greatly improved.
Disclosure of Invention
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the additive is an organic polymer nitro compound.
The additive is added into an organic electrolyte of an alkali metal battery, the mass fraction of the additive in the organic solvent is 0.1-10%, and the mass fraction of the supporting electrolyte in the organic solvent is 15-87%. Preferably, the additive accounts for 1-5% of the mass of the organic solvent, and the supporting electrolyte accounts for 15-50% of the mass of the organic solvent.
The high-molecular nitro compound is one or more than two of polyethylene glycol nitrate, nitrocellulose (cellulose nitrate), polyvinyl alcohol nitrate and polyglycidyl ether nitrate; the average molecular weight is 2000-100000, preferably 20000-80000;
wherein: the nitrogen content of the nitrated polyethylene glycol is 2-15%; the nitrogen content of the polyglycidyl ether nitrate is 2-13%; the nitrogen content of the polyvinyl alcohol nitrate is 2-16 wt%; the nitrogen content of the nitrocellulose is 2 to 14wt%, and the nitrogen content of the nitrocellulose is preferably 9 to 14%.
The organic polymer nitro-compound is nitrocellulose with the nitrogen content of 9-14%.
The organic solvent is an organic solvent of ester, ether, sulfone, ketone and nitrile, and comprises the following components: one or more than two of 1, 3-dioxolane, 1, 4-dioxane, ethylene oxide, ethylene glycol dimethyl ether, methyl ethyl ether, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, acetonitrile, succinonitrile, sulfolane, dimethyl sulfoxide and cyclobutanone; preferably one or more than two of 1, 3-dioxolane, ethylene glycol dimethyl ether, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate;
the supporting electrolyte is one or more than two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorosulfonate imide, lithium perchlorate, sodium hexafluorophosphate and potassium hexafluorophosphate.
The preparation method of the additive comprises the following steps:
(1) dissolving the required supporting electrolyte in an organic solvent to obtain a uniform solution;
(2) dissolving the required organic polymer nitro compound as an additive in the solution, and uniformly stirring to obtain the required organic electrolyte;
the additive accounts for 0.1 to 10 percent of the mass fraction of the organic solvent;
the supporting electrolyte accounts for 15-87% of the organic solvent by mass.
The additive is used in an alkali metal battery, preferably in a lithium metal negative electrode.
The negative electrode of the alkali metal battery is alkali metal (such as metal lithium, metal sodium and metal potassium); the positive electrode can be made of corresponding metal ion electrode materials (such as lithium iron phosphate, lithium cobaltate, nickel-cobalt-manganese ternary materials, sodium vanadium phosphate, sodium manganate, sodium pyrophosphate, potassium vanadium phosphate, potassium vanadium fluorophosphate and the like) or sulfur positive electrodes; the electrolyte is one or more of ethers, esters, sulfones, ketones and nitriles.
The beneficial results of the invention are:
the invention relates to a film-forming additive for regulating alkali metal deposition,
(1) organic high-molecular nitrate is added into the electrolyte and used as a reactant to participate in the generation of an electrode/electrolyte interface film, so that the continuous reaction and consumption of the electrolyte and alkali metal are effectively inhibited, the nitro functional groups on the high-molecular nitrate can be reduced in situ on the surface of lithium metal, and the generated product is a polymer-inorganic layer, so that the high-ionic conductivity is realized, the interface ion transmission is greatly accelerated, and the alkali ion deposition uniformity is improved. Meanwhile, the polymer framework can react in situ to generate a compact organic film, the organic framework covers the surface of lithium, and the long-chain organic framework has good flexibility and viscosity, so that the inorganic layer fracture caused by volume expansion of the negative electrode can be effectively relieved, the growth of dendritic crystals can be effectively inhibited, and the circulation stability of the lithium battery is remarkably improved.
(2) The organic nitro compound is dissolved in the organic electrolyte, and can be applied to lithium metal cathodes and batteries using alkali metals such as sodium ions and potassium ions as cathodes, and the anodes can be matched with corresponding alkali metal ion anode materials, sulfur anode materials and the like.
(3) Compared with lithium nitrate, the high-molecular nitric acid ester provided by the invention can be dissolved in ether electrolyte and various organic electrolytes to regulate and control the deposition reversibility of lithium metal, so that the application range of the high-molecular nitric acid ester is greatly widened.
(4) Compared with a flexible membrane formed by small-molecular organic nitrate and high-molecular nitrate, the high-molecular nitrate can construct a flexible and rigid organic/inorganic interface membrane with high ionic conductivity on the surface of lithium, so that dendritic crystal growth can be effectively inhibited, and the cycle stability is improved. By adding the high-molecular nitrate into the electrolyte, the high-molecular nitrate is used as a reactant to participate in the generation of an electrode/electrolyte interface film, so that the continuous reaction and consumption of the electrolyte and alkali metal are effectively inhibited, and the cycling stability of the battery is improved.
(5) The nitro functional group on the high molecular nitrate can be reduced in situ on the metal surface, and the generated product has higher ionic conductivity compared with the decomposition products of lithium nitrate and small molecular nitro compounds, thereby greatly accelerating the transmission of interfacial ions and better improving the uniformity of ion deposition.
Drawings
FIG. 1: the action mechanism of the high-molecular nitro compound in the lithium electrode;
FIG. 2: examples 1-3 schematic structural diagrams of nitrocellulose;
FIG. 3: examples 1-3 infrared spectra of nitrocellulose;
FIG. 4: cycling performance of lithium metal symmetric batteries of comparative examples 1,4 and examples 1, 2;
FIG. 5: cycling performance of the lithium metal symmetric batteries of comparative example 2 and example 2;
FIG. 6: cycling performance of the lithium metal symmetric batteries of comparative examples 5, 6 and example 5;
FIG. 7: lithium metal electrodes of comparative examples 5 and 6 at 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) surface topography after 10 cycles of deposition.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
Weighing required nitrocellulose with the nitrogen content of 10.3 percent and the average molecular weight of 80000), dissolving in the ether electrolyte in the comparative example 1, and preparing the nitrocellulose-ether electrolyte with the mass fraction of 1 percent. A lithium | lithium symmetric cell was assembled according to the method of comparative example 1. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Example 2
The required nitrocellulose (nitrogen content 10.3%, average molecular weight 80000) was weighed and dissolved in the ether electrolyte in comparative example 1, and a nitrocellulose-ether electrolyte containing 5% by mass was prepared. A lithium | lithium symmetric cell was assembled according to the method of comparative example 1. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Example 3
The required nitrocellulose (nitrogen content 10.3%, average molecular weight 80000) was weighed and dissolved in the ester electrolyte in comparative example 5, and a nitrocellulose-ester electrolyte containing 5% by mass was prepared. A lithium | lithium symmetric cell was assembled according to the method of comparative example 5. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Example 4
The required nitrated polyethylene glycol (with 12% nitrogen content and average molecular weight of 60000) was weighed and dissolved in the ester electrolyte in comparative example 5, and a nitrated polyethylene glycol-ester electrolyte containing 5% by mass was prepared. A lithium | lithium symmetric cell was assembled according to the method of comparative example 5. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (2) is subjected to charge-discharge cycles.
Example 5
The required polyvinyl alcohol nitrate (with a nitrogen content of 12% and an average molecular weight of 60000) was weighed and dissolved in the ester electrolyte in comparative example 5, and a polyvinyl alcohol nitrate-ester electrolyte containing 5% by mass was prepared. A lithium | lithium symmetric cell was assembled according to the method of comparative example 5. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Example 6
The required polyglycidyl ether nitrate (with the nitrogen content of 10% and the average molecular weight of 20000) is weighed and dissolved in the ester electrolyte in the comparative example 5, and the polyglycidyl ether nitrate-ester electrolyte with the mass fraction of 5% is prepared. A lithium | lithium symmetric cell was assembled according to the method of comparative example 5. 1mA5/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Comparative example 1
1M lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) is used as a supporting electrolyte, and a mixed solution (volume ratio is 1:1) of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) is used as a blank ether electrolyte. A lithium sheet with the diameter of 1.6mm and a celgard 2325 diaphragm are used to assemble the lithium | lithium symmetrical battery. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (2) is subjected to charge-discharge cycles.
Comparative example 2
1M lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) is used as a supporting electrolyte, a mixed solution (volume ratio is 1:1) of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) is used as an electrolyte, 1 wt% of lithium nitrate is added to be used as an additive, a lithium sheet with the diameter of 1.6mm is used, and celgard 2325 is used as a diaphragm, so that the lithium | lithium symmetric battery is assembled. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Comparative example 3
Weighing required isosorbide dinitrate, dissolving the isosorbide dinitrate in the ether electrolyte in the comparative example 1, and preparing the isosorbide dinitrate-ether electrolyte with the mass fraction of 1%. A lithium | lithium symmetric cell was assembled according to the method of comparative example 1. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Comparative example 4
The required cellulose (average molecular weight 80000) was weighed and dissolved in the ether electrolyte in comparative example 1, and a cellulose-ether electrolyte containing 1% by mass was prepared. A lithium | lithium symmetric cell was assembled according to the method of comparative example 1. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Comparative example 5
With 1M lithium hexafluorophosphate (LiPF) 6 ) For supporting electrolyte, a mixed solution (volume ratio is 1:1) of Ethylene Carbonate (EC) and diethyl carbonate (DEC) is used as a solvent as a blank ester electrolyte, a lithium sheet with the diameter of 1.6mm is used, and celgard 2325 is used as a diaphragm, so that the lithium | lithium symmetrical battery is assembled. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Comparative example 6
The required polyglycidyl ether nitrate (with a nitrogen content of 10% and an average molecular weight of 1000) was weighed and dissolved in the ester electrolyte in comparative example 5, and a polyglycidyl ether nitrate-ester electrolyte containing 5% by mass was prepared. A lithium | lithium symmetric cell was assembled according to the method of comparative example 5. 1mA/cm 2 At a current density of 1mAh/cm 2 The deposition dissolution capacity of (a) is subjected to charge-discharge cycles.
Comparative example 7
The required polyglycidyl ether nitrate (with a nitrogen content of 10% and an average molecular weight of 800000) was weighed and dissolved in the ester electrolyte of comparative example 5, and a polyglycidyl ether nitrate-ester electrolyte containing 1% by mass of the electrolyte was prepared. However, the polyglycidyl ether nitrate is not easy to dissolve, the viscosity of the electrolyte is too high, the polarization of the battery is large, and the polyglycidyl ether nitrate is not suitable for being used as the electrolyte.
FIG. 1 shows the action mechanism of the high molecular nitro compound in the graphite electrode. The nitrocellulose polymer skeleton structure covers the surface of lithium, can adapt to the volume change in the deposition and dissolution process of lithium metal, and simultaneously inhibits the reaction of electrolyte and lithium metal; and the nitro group of the branched chain is connected with lithium metal, so that the falling-off of the macromolecular framework is prevented. Meanwhile, the nitrocellulose has lithium affinity, and the reduction product of the nitro group has high ionic conductivity, which is beneficial to the conduction of lithium ions at an interface.
FIG. 2 is a schematic diagram of nitrocellulose structure. The experiment researches the influence of different organic polymer nitro compounds on the lithium metal battery in ether and ester electrolytes. The structure of the nitrocellulose is characterized by infrared spectrum3, ONO is obvious in the infrared spectrum 2 Peaks, demonstrating that the additive used was nitrocellulose. As can be seen from fig. 4, 5 and 6, the addition of the organic polymer nitro compound to the electrolyte can significantly improve the cycling stability of lithium deposition dissolution. As can be seen from FIGS. 4 and 5, under the conditions of current density of 1mA/cm2 and deposition capacity of 1mAh/cm2, the polarization voltage of the lithium symmetrical cell without the nitro compound in the electrolyte is increased to 120mV after circulation for 150h, and is reduced after 200h, so that micro short circuit occurs; after the cellulose and the lithium nitrate are added, the stability of the battery is improved, but the polarization is obviously increased in the later period of the cycle. After the nitrocellulose is added, the cycling stability of the lithium metal battery is improved, the polarization voltage is reduced, and the cycling life of the battery is further prolonged along with the increase of the content of the nitrocellulose. The 5% nitrocellulose is added, the battery can stably circulate for 550h, the voltage polarization is small, presumably because the nitro functional group on the nitrate can be reduced on the lithium surface in situ, the product has high ionic conductivity, the interface ion transmission is greatly accelerated, and the ion deposition uniformity is improved. Meanwhile, the polymer skeleton can react in situ to generate an organic matter compact film which covers the surface of lithium, and the organic matter compact film has good flexibility and viscosity and can effectively relieve inorganic layer fracture caused by volume expansion of the negative electrode, so that dendritic crystal growth is inhibited.
Experiments further explore the influence of organic polymer nitro compounds on the electrochemical properties of esters. As can be seen from FIG. 6, the addition of 5% of the polyglycidyl ether nitrate performed optimally (after 220h cycling, the voltage stabilized at 80mV), while the short chain polyglycidyl ether nitrate did not completely cover the lithium surface and the cycling stability was poor.
And (4) exploring the lithium deposition morphology by utilizing SEM. As can be seen from fig. 7, in the ether electrolyte, after 10 cycles of charge and discharge under the conditions of a current density of 1mA/cm2 and a specific capacity of 1mAh/cm2, the surface of the lithium metal electrode containing no organic polymer nitro compound in the electrolyte is uneven and is in a moss shape, the specific surface area of the lithium electrode is large, and the electrolyte is continuously consumed, so that the polarization voltage of the lithium symmetric battery is increased. After the polyglycidyl ether nitric acid is added, the surface is uniform and flat, a film is generated on the surface of lithium, and the growth of lithium dendrite is inhibited.

Claims (7)

1. Use of an electrolyte in an alkali metal battery, the battery electrolyte comprising a supporting electrolyte dissolved in an organic solvent; the method is characterized in that: wherein the electrolyte is also added with an additive; the additive is a high-molecular nitro compound which can be dissolved in the electrolyte of the alkali metal battery, and the average molecular weight is 20000-80000; the high-molecular nitro compound is one or two of cellulose nitrate and polyglycidyl ether nitrate; wherein: the nitrogen content of the polyglycidyl ether nitrate is 10-13%; the nitrogen content of the cellulose nitrate is 9-14 wt%; the additive accounts for 1-5% of the organic solvent by mass; the additive is added into the electrolyte of the alkali metal battery, and the battery electrolyte comprises the additive dissolved in an organic solvent and a supporting electrolyte; the supporting electrolyte accounts for 15-50% of the organic solvent by mass.
2. The application of the electrolyte as claimed in claim 1, wherein the electrolyte adopts one or more organic solvents selected from ester, ether, sulfone, ketone and nitrile;
the supporting electrolyte is one or more than two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonyl imide, lithium perchlorate, sodium hexafluorophosphate and potassium hexafluorophosphate.
3. The use according to claim 2,
the electrolyte adopts organic solvents as follows: 1, 3-dioxolane, 1, 4-dioxane, ethylene oxide, ethylene glycol dimethyl ether, methyl ethyl ether, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, acetonitrile, succinonitrile, sulfolane, dimethyl sulfoxide and one or more of cyclobutanone.
4. A use as claimed in any one of claims 1 to 3, comprising the steps of:
(1) dissolving the required supporting electrolyte in an organic solvent to obtain a uniform solution;
(2) and dissolving the required organic polymer nitro compound serving as an additive in the solution, and uniformly stirring to obtain the required organic electrolyte.
5. Use according to claim 1, characterized in that: the electrolyte is applied to an alkali metal battery with a lithium metal cathode.
6. Use according to claim 5, characterized in that: the cathode of the alkali metal battery is alkali metal of metal lithium, metal sodium or metal potassium; the positive electrode can use a corresponding metal ion electrode material or a sulfur positive electrode; the organic solvent is one or more of ethers, esters, sulfones, ketones and nitriles.
7. Use according to claim 6, characterized in that: the anode uses corresponding metal ion electrode materials including one or more of lithium iron phosphate, lithium cobaltate, nickel cobalt manganese ternary materials, sodium vanadium phosphate, sodium manganate, sodium pyrophosphate, potassium vanadium phosphate and potassium vanadium fluorophosphate.
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