CN111129593A - Additive of secondary lithium metal battery electrolyte, electrolyte and preparation method - Google Patents

Additive of secondary lithium metal battery electrolyte, electrolyte and preparation method Download PDF

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CN111129593A
CN111129593A CN201911360027.0A CN201911360027A CN111129593A CN 111129593 A CN111129593 A CN 111129593A CN 201911360027 A CN201911360027 A CN 201911360027A CN 111129593 A CN111129593 A CN 111129593A
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additive
electrolyte
lithium metal
metal battery
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党岱
付祥祥
吴传德
曾燃杰
安璐
陈超
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Guangdong University of Technology
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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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses an additive of an electrolyte of a secondary lithium metal battery, the electrolyte and a preparation method thereof. The concentration of the lithium salt in the electrolyte of the lithium metal secondary battery is 1-5 mol/L, the additive comprises an additive A and an additive B, and the additive A is pentachlorothiophene dicarboxylic acid C5H3ClO2S and the like, the mass percentage content of the additive B in the electrolyte is 0.1-5 percent, and the additive B is lithium nitrate LiNO3And the mass percentage content in the electrolyte is 1 to 5 percent. The electrolyte provided by the invention can protect the lithium metal cathode to a great extent, is easy for large-scale production and is suitable for lithium metal secondary batteries.

Description

Additive of secondary lithium metal battery electrolyte, electrolyte and preparation method
Technical Field
The invention relates to the field of electrochemistry, in particular to an additive of an electrolyte of a secondary lithium metal battery, the electrolyte and a preparation method.
Background
The deposition of dendrite-free lithium metal is a fundamental requirement for maintaining the safety of lithium metal batteries. In order to solve the problem of dendritic crystal growth of lithium metal, researchers at home and abroad have already made a lot of modification work. Professor of poplar bin, university of beijing aerospace materials institute, adopts a Vertically Oriented Lithium-Copper-Lithium array composite electrode to achieve Lithium ion current distribution and electric field distribution in the electrode, and simultaneously plays a role of a 'dam', guides uniform deposition of Lithium, effectively buffers volume change of deposited Lithium in a circulation process, and effectively inhibits formation of Lithium dendrites (dedrite-Free Lithium antibodies with Ultra-Deep drawing and Plating Properties Based on vertical organic Lithium-Copper-Lithium alloys, adv.mater, 2019,31, 1901310). The method designs Ni by utilizing an ion nitriding technology by the professor chenjiangzhu and the professor Sunjing of southeast university3The N modified nickel foam (PNNF) is used as a 3D current collector of the lithium negative electrode. Generating a layer of Ni on the surface of the foamed nickel by plasma in nitrogen atmosphere3N, Ni after electrodeposition of lithium metal3Conversion of N to Li3N, due to the high ionic conductivity and excellent Lithium affinity of the two, Lithium Metal can be uniformly deposited and extracted on the surface of the current collector, and the generation of dendrite is effectively inhibited (Lithium Metallic nitride Modified Nickel Foam for Stable Lithium Metal Anode, Energy Storage Materials,2019, DOI: 10.1016/j.ensm.2019.04.005). In addition, professor marijun of the institute of chemistry of Chinese academy of sciences and professor Guo Yue develop a self-supporting flexible three-dimensional Nitrogen-Doped Carbon foam (NGCF) with a three-dimensional porous skeleton structure, which can relieve volume change in a circulation process, and Nitrogen-containing functional groups of the light Carbon foam can regulate initial Nucleation of Lithium, further induce subsequent Lithium to grow uniformly and inhibit Lithium dendrite formation (Uniform Lithium Nuclear/grown Induced by light weight Nitrogen-Doped Carbon foam or High-Performance Lithium Metal Anodes, adv.Mater, 2018,30, 1706216). The above-mentioned researchAlthough a new idea is provided for solving the problem of dendritic crystal growth of the lithium metal, the operation process is complicated and the industrialization is not facilitated. In the prior art, a passivation layer is formed on a lithium metal negative electrode by adding an additive containing lithium ions, the lithium ion content of an electrolyte is increased, and the conductivity of the electrolyte is improved, but excessive lithium ions need to be added, and the cost is too high.
Disclosure of Invention
The invention provides an additive of a secondary lithium metal battery electrolyte and a secondary lithium metal battery electrolyte for overcoming at least one defect in the prior art, and can solve the problems of poor cycle performance, low coulombic efficiency, poor safety and the like caused by dendritic crystal growth in the charge-discharge cycle process of a metal lithium secondary battery cathode only by adding the additive; also provides a preparation method and application of the electrolyte of the secondary lithium metal battery, and the operation process is simple and convenient for industrialization.
The purpose of the invention is realized by the following technical scheme.
An additive of electrolyte of secondary lithium metal battery comprises an additive A and an additive B, wherein the additive A is pentachlorothiophene dicarboxylic acid C5H3ClO2S, dithiophene carboxylic acid C5H4O2S, dipentathiophenedicarboxylic acid C6H4O4S, and the additive B is lithium nitrate LiNO3Lithium phosphate Li3PO4One kind of (1).
A secondary lithium metal battery electrolyte comprises a lithium salt and an organic solvent, and further comprises an additive of the secondary lithium metal battery electrolyte.
The additive A is a lithium metal negative electrode film-forming additive and can form a stable solid electrolyte interface film (SEI film) on the surface of an anode in the initial cycle period of the battery; the additive B can stabilize a lithium metal interface, and the additive A and the additive B are cooperatively matched, so that dendritic crystal growth of Li metal is effectively inhibited in the reciprocating deposition/stripping process, the cycle performance of the battery is improved, and the safety of the lithium metal secondary battery is greatly improved. The electrolyte provided by the invention only needs to be added with an additive, so that the cation concentration near the lithium metal body is increased, and the lithium ion concentration can be increased.
Preferably, the mass percentage content of the additive A is 0.1-5%, and the mass percentage content of the additive B is 1-5%. Realizes the inhibition of lithium dendrite, and does not form moss-shaped, linear and dendritic metallic lithium dendrite on the lithium/electrolyte interface.
Preferably, the mass percent of the additive A is 2%, and the mass percent of the additive B is 2%. The stability and the cycle life of the lithium metal battery are remarkably improved, and the excellent electrochemical performance is shown.
Preferably, the organic solvent includes one or a combination of two or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), dimethyl carbonate (DMC), ethyl methyl carbonate (MEC), Methyl Propyl Carbonate (MPC), diethyl carbonate (DEC), 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), or diethylene glycol Dimethyl Ether (DEDM).
Preferably, the lithium salt comprises LiBF4、LiAsO6、LiPF6、LiTFSI、LiCF3SO3Or Li3AlF6One or a combination of two or more of them.
Preferably, the concentration of the lithium salt is 1-5 mol/L.
The invention also provides a preparation method of the electrolyte of the secondary lithium metal battery, which comprises the following steps:
(1) under the protection of inert gas, dissolving the lithium salt in the organic solvent to form a lithium salt electrolyte;
(2) and adding an additive A and an additive B into the lithium salt electrolyte, and fully and uniformly stirring to obtain the electrolyte.
The invention also provides a secondary lithium metal battery, which comprises a positive electrode, an elastic sheet, a gasket, a diaphragm, a negative electrode and the electrolyte of the secondary lithium metal battery.
Preferably, the anode and cathode materials are LiFePO4、LiV3(PO4)3、LixCoO2、LiyMnO2、mLiMnO2·(1-m)LiAO2、LiNibCoaMn1-aO2、LiNi0.5Mn1.5O4、Li2TiO3、FeF3·jH2At least one of O, S, Se, Li, Cu, metal oxide or metal sulfide, wherein x is more than or equal to 0.4 and less than or equal to 1, y is more than or equal to 0.4 and less than or equal to 1, and 0<m<1, A is one of Ni, Co, Mn, Al and Fe, b is more than or equal to 0.5 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 0.2, and j is more than or equal to 0 and less than or equal to 0.5.
Preferably, the membrane is selected from one or a combination of more than two of GF membrane, PE membrane, PP/PE membrane or PP/PE/PP membrane.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the additive A and the additive B are added into the electrolyte, so that the growth of metallic lithium dendrites can be inhibited, and moss-shaped, linear and dendritic metallic lithium dendrites are not formed on a lithium/electrolyte interface.
(2) In the circulation process of the metal lithium secondary battery, the electrolyte can form a stable solid electrolyte layer containing inorganic salt on the surface of the metal lithium cathode, and the growth of dendrite is inhibited in the reciprocating deposition process, so that the safety of the metal lithium secondary battery is greatly improved.
(3) The invention does not need to charge and discharge under specific current density, does not need to add complex compounds or solvents to stabilize the negative electrode, has simple operation process and is convenient for industrialization.
Drawings
FIG. 1 is an SEM image of the surface of lithium metal after charge-discharge cycling for the battery of example 1 containing the double salt additive;
FIG. 2 is an SEM image of a lithium metal surface after a charge-discharge cycle without additive of comparative example 1;
FIG. 3 is a charge-discharge voltage/time curve diagram of a symmetric Li | Li battery assembled by adding an additive and a lithium metal cathode without the additive into an electrolyte;
FIG. 4 is a graph of charge-discharge first-turn capacity-voltage of a Li | | | Cu battery;
fig. 5 is a charge-discharge curve diagram of a Li | | | Cu battery assembled by a metal lithium negative electrode and a copper foil with and without an additive added to an electrolyte.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
(1) Preparation of the electrolyte
Storing the commercial LiTFSI under the protection of high-purity argon atmosphere for later use;
will purchase C5H3ClO2S,LiNO3Preserving under the protection of high-purity argon atmosphere for later use;
under the protection of a high-purity argon atmosphere, adding DOL and DME in a volume ratio of 1: mixing the mixture according to the proportion of 1 to obtain a mixed solvent, dissolving the LiTFSI into the mixed solvent, and fully stirring to prepare a 1mol/L LiTFSI/(DOL + DME) solution.
Taking a proper amount of commercial C5H3ClO2S，LiNO3Dissolving the mixture in the prepared LiTFSI/(DOL + DME) solution, and fully and uniformly stirring to obtain the solution containing 2% of C5H3ClO2S+2％LiNO31mol/L of LiTFSI/(DOL + DME) electrolyte of the additive.
(2) Assembly of battery
①, assembling a Li symmetric battery under the protection of a high-purity argon atmosphere by using metal lithium as a positive electrode material and a negative electrode material, a PE film as a diaphragm, and the LiTFSI/(DOL + DME) electrolyte prepared in the step (1) of the present embodiment as an electrolyte.
② A Li | | Cu battery is assembled under the protection of a high-purity argon atmosphere by using copper foil as a positive electrode material, using metal lithium as a negative electrode material, using a PE film as a diaphragm, and using the LiTFSI/(DOL + DME) electrolyte prepared in the step (1) of the embodiment as an electrolyte.
(3) Electrochemical performance test
① at 1mAh/cm2Volume, 1mA/cm2And (3) carrying out charge-discharge cycle test on the Li | Li symmetrical battery in ① in the step (2) by using the current density.
② at 1mAh/cm2Deposition capacity, 1mA/cm2Current density, 1And (3) carrying out charge-discharge cycle test on the Li | | | Cu battery in ② in the step (2) by using the charging voltage of V.
Example 2
The difference between this example and example 1 is that C5H4O2S is 0.1%, LiNO3Is 1%.
Under the protection of a high-purity argon atmosphere, EC and DMC are mixed according to the volume ratio of 2: 3 proportion to obtain mixed solvent, and mixing LiPF6Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare 3mol/L LiPF6V (EC + DMC) solution.
Taking a proper amount of commercial C5H4O2S，LiNO3Dissolved in LiPF prepared as described above6V (EC + DMC) solution, and stirring well to obtain a solution containing 0.1% C5H4O2S+1％LiNO33mol/L LiPF of additive6/(EC + DMC) electrolyte. The test method was the same as in example 1.
Example 3
The difference between this example and example 1 is that C6H4O4S is 2%, Li3PO4The content was 5%.
Mixing VC and MEC according to the volume ratio of 3:1 under the protection of high-purity argon atmosphere to obtain a mixed solvent, and mixing LiBF4Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare 2mol/L LiBF4V (VC + MEC) solution.
Taking a proper amount of commercial C5H3ClO2S，LiNO3Dissolving the mixture in the prepared LiTFSI/(DOL + DME) solution, and fully and uniformly stirring to obtain the solution containing 2% of C6H4O4S+5％Li3PO42mol/L LiBF of additive4V (VC + MEC) electrolyte. The test method was the same as in example 1.
Example 4
The difference between this example and example 1 is that C5H3ClO2S is 2.5%, LiNO3The content was 2%.
Mixing PC and DEC at a volume ratio of 1:2 under the protection of high-purity argon atmosphere to obtain mixed solvent, and mixing LiCF3SO3Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare LiCF with the concentration of 5mol/L3SO3V (PC + DEC) solution.
Taking a proper amount of commercial C5H3ClO2S，LiNO3Dissolving in the prepared LiCF3SO3/(PC + DEC) solution, and stirring to obtain solution containing 2.5% C5H3ClO2S+2％LiNO3Additive LiCF of 5mol/L3SO3/(PC + DEC) electrolyte. The test method was the same as in example 1.
Example 5
The difference between this example and example 1 is that C5H4O2S is 5%, Li3PO4Is 0.5%.
Under the protection of high-purity argon atmosphere, DOL and DEDM are mixed according to the volume ratio of 1:5 to obtain a mixed solvent, and LiAsO is added6Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare 4mol/L LiAsO6V (DOL + DEDM) solution.
Taking a proper amount of commercial C5H4O2S，Li3PO4Dissolved in the above prepared LiAsO6/(DOL + DEDM) solution, and thoroughly stirred to homogeneity to give a solution containing 0.5% C5H4O2S+5％Li3PO44mol/L LiAsO of additive6/(DOL + DEDM) electrolyte. The test method was the same as in example 1.
TABLE 1 test results for examples 1-5
Figure BDA0002336944230000061
In conclusion, the electrolyte containing 2% of the additive is obtained by testing and selecting the additives in different proportions, so that the inhibition on lithium dendrite is realized to the greatest extent, and moss-shaped, linear and dendritic metal lithium dendrites are not formed on a lithium/electrolyte interface. The addition of the additive remarkably improves the stability and the cycle life of the lithium metal battery, and shows excellent electrochemical performance.
Comparative example 1
This comparative example differs from example 1 in that: the electrolyte of comparative example 1 was the additive-free LiTFSI/(DOL + DME) solution described in step (1) of this example.
After the cell was disassembled for 100 cycles and repeatedly rinsed with electrolyte solvent, fig. 1 is an SEM image of the lithium metal surface after charge-discharge cycles with the double salt additive of example 1; FIG. 2 is an SEM image of a lithium metal surface after a charge-discharge cycle without additive of comparative example 1; in comparison of fig. 1 to fig. 2, it can be observed that the surface of the lithium metal containing the double salt additive electrolyte is very flat with no lithium dendrites present, indicating that the additive effectively suppresses the growth of dendrites.
Tests have found that the current density is 1mA/cm2The deposition capacity is 1mAh/cm2Under the condition, as shown in fig. 3, after 50 hours of circulation, the voltage of the symmetrical battery assembled by the electrolyte without the additive is rapidly increased and increased to 400mV in a short time, then the voltage is severely fluctuated, the battery fails after about 170 hours of circulation, and the battery is broken, while the Li I Li symmetrical battery containing the additive can stably circulate for 1000 hours under the hysteresis voltage of 17mV, and has an ultra-long cycle life. As shown in fig. 4, it was found that the hysteresis voltage of the battery containing the additive was significantly lower than that of the battery containing no additive.
As can be seen from FIG. 5, the Li | | | Cu cell is at 1mA/cm2The current density is 1mAh/cm2Coulombic efficiency at the deposition amount, the battery containing the additive was able to stably cycle for 100 cycles at 91% coulombic efficiency, indicating that the lithium battery to which the electrolyte additive was added showed extremely stable cycle performance.
Comparative example 2
The difference between this example and example 1 is that C5H3ClO2S is 5%, LiNO is not added3。
Under the protection of a high-purity argon atmosphere, EC and DMC are mixed according to the volume ratio of 2: 3 proportion to obtain mixed solvent, and mixing LiPF6Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare 3mol/L LiPF6V (EC + DMC) solution.
Taking a proper amount of commercial C5H3ClO2S is dissolved in the prepared LiPF6V (EC + DMC) solution, and stirring well to obtain a solution containing 0.1% C5H3ClO2S+1％LiNO33mol/L LiPF of additive6/(EC + DMC) electrolyte.
Comparative example 3
This example is different from example 1 in that LiNO35% without C5H3ClO2S。
Under the protection of a high-purity argon atmosphere, EC and DMC are mixed according to the volume ratio of 2: 3 proportion to obtain mixed solvent, and mixing LiPF6Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare 3mol/L LiPF6V (EC + DMC) solution.
Taking a proper amount of commercially available LiNO3Dissolved in LiPF prepared as described above6V (EC + DMC) solution, and stirring well to obtain a solution containing 0.1% C5H3ClO2S+1％LiNO33mol/L LiPF of additive6/(EC + DMC) electrolyte.
Comparative example 4
This example is different from example 1 in that LiNO36% of C5H3ClO2S is 6%.
Under the protection of a high-purity argon atmosphere, EC and DMC are mixed according to the volume ratio of 2: 3 proportion to obtain mixed solvent, and mixing LiPF6Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare 3mol/L LiPF6V (EC + DMC) solution.
Taking a proper amount of commercially available LiNO3Dissolved in LiPF prepared as described above6V (EC + DMC) solution, and stirring well to obtain a solution containing 0.1% C5H3ClO2S+1％LiNO33mol/L LiPF of additive6/(EC + DMC) electrolyte.
Comparative example 5
This example is different from example 1 in that LiNO30.1% of C5H3ClO2S is 0.01%.
Under the protection of a high-purity argon atmosphere, EC and DMC are mixed according to the volume ratio of 2: 3 proportion to obtain mixed solvent, and mixing LiPF6Dissolving the mixture into the mixed solvent, fully stirring the mixture to prepare 3mol/L LiPF6V (EC + DMC) solution.
Taking a proper amount of commercially available LiNO3Dissolved in LiPF prepared as described above6V (EC + DMC) solution, and stirring well to obtain a solution containing 0.1% C5H3ClO2S+1％LiNO33mol/L LiPF of additive6/(EC + DMC) electrolyte.
The test method was the same as in examples 1 to 5.
TABLE 2 test results of comparative examples 2 to 5
Figure BDA0002336944230000081
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The additive of the secondary lithium metal battery electrolyte is characterized by comprising an additive A and an additive B, wherein the additive A is pentachlorothiophene dicarboxylic acid C5H3ClO2S, dithiophene carboxylic acid C5H4O2S, dipentathiophenedicarboxylic acid C6H4O4S, and the additive B is lithium nitrate LiNO3Lithium phosphate Li3PO4One kind of (1).
2. A secondary lithium metal battery electrolyte comprising a lithium salt, an organic solvent, and an additive for the secondary lithium metal battery electrolyte of claim 1.
3. The electrolyte for a secondary lithium metal battery according to claim 2, wherein the additive A is contained in an amount of 0.1 to 5% by mass, and the additive B is contained in an amount of 1 to 5% by mass.
4. The electrolyte for a secondary lithium metal battery according to claim 2, wherein the additive a is 2% by mass and the additive B is 2% by mass.
5. The electrolyte for a secondary lithium metal battery according to claim 2, wherein the organic solvent comprises one or a combination of two or more of ethylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, diethyl carbonate, 1, 3-dioxolane, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether.
6. The secondary lithium metal battery electrolyte of claim 2, wherein the lithium salt comprises LiBF4、LiAsO6、LiPF6、LiTFSI、LiCF3SO3Or Li3AlF6One or a combination of two or more of them.
7. The electrolyte for a secondary lithium metal battery according to claim 6, wherein the concentration of the lithium salt is 1 to 5 mol/L.
8. A method for preparing the electrolyte of a secondary lithium metal battery according to claim 2, comprising the steps of:
(1) under the protection of inert gas, dissolving the lithium salt in the organic solvent to form a lithium salt electrolyte;
(2) and adding an additive A and an additive B into the lithium salt electrolyte, and fully and uniformly stirring to obtain the electrolyte.
9. A secondary lithium metal battery comprising a positive electrode and a negative electrode, characterized by further comprising the secondary lithium metal battery electrolyte of claim 2.
10. The secondary lithium metal battery of claim 9, wherein the positive electrode and the negative electrode are LiFePO4、LiV3(PO4)3、LixCoO2、LiyMnO2、mLiMnO2·(1-m)LiAO2、LiNibCoaMn1-aO2、LiNi0.5Mn1.5O4、Li2TiO3、FeF3·jH2One or more of O, S, Se, Li, Cu, metal oxide or metal sulfide, wherein x is more than or equal to 0.4 and less than or equal to 1, y is more than or equal to 0.4 and less than or equal to 1, and 0<m<1, A is one of Ni, Co, Mn, Al and Fe, b is more than or equal to 0.5 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 0.2, and j is more than or equal to 0 and less than or equal to 0.5.
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CN112467218A (en) * 2020-12-01 2021-03-09 郑州大学 Lithium metal battery based on copper nitrate electrolyte additive
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CN114421010A (en) * 2020-10-28 2022-04-29 陕西泽邦环境科技有限公司 Lithium-supplement type lithium ion battery electrolyte and application thereof

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CN112467218A (en) * 2020-12-01 2021-03-09 郑州大学 Lithium metal battery based on copper nitrate electrolyte additive
CN114094180A (en) * 2021-11-22 2022-02-25 浙江工业大学 Ether electrolyte containing silver nitrate additive for lithium metal battery

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