CN112670574A - Electrolyte for metal battery and metal battery - Google Patents
Electrolyte for metal battery and metal battery Download PDFInfo
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- CN112670574A CN112670574A CN202011525861.3A CN202011525861A CN112670574A CN 112670574 A CN112670574 A CN 112670574A CN 202011525861 A CN202011525861 A CN 202011525861A CN 112670574 A CN112670574 A CN 112670574A
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- lithium
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- metal battery
- negative electrode
- salt
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 105
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 5
- 150000001621 bismuth Chemical class 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002290 germanium Chemical class 0.000 claims abstract description 5
- 150000002471 indium Chemical class 0.000 claims abstract description 5
- -1 nickel cobalt aluminum Chemical compound 0.000 claims description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 239000011244 liquid electrolyte Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 238000005137 deposition process Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 3
- 229910052718 tin Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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 provides an electrolyte for a metal battery and the metal battery, and belongs to the technical field of batteries. The electrolyte for a metal battery provided by the invention comprises: the electrolyte additive is one or more of indium salt, tin salt, bismuth salt and germanium salt. Since metals such as indium, tin, and bismuth have a higher electrode potential than lithium, these metal ions can be reduced on the surface of the negative electrode by lithium, thereby forming an SEI film containing metal components in situ on the surface of the lithium negative electrode. In the circulation process, metal ions in the electrolyte have electrochemical activity, the stability of a metal protective layer on the surface of the lithium negative electrode is promoted, the metals can store lithium in an alloy forming mode, and meanwhile, the formed alloy can reduce a diffusion barrier in the lithium deposition process, promote the rapid migration of the lithium ions, inhibit the growth of lithium dendrites, and further improve the circulation stability of the lithium metal negative electrode.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an electrolyte for a metal battery and the metal battery.
Background
With the progress of science and technology and society, people have more and more demands on efficient energy storage and conversion devices. The lithium ion battery has the advantages of high energy density, long cycle life, no memory effect and the like, is widely concerned, is successfully applied to different fields such as smart phones, electric automobiles, power grid energy storage and the like, and is dominant in the current battery market. At present, the negative electrode material of a commercial lithium ion battery is mainly graphite, the theoretical specific capacity of the negative electrode material is 372mAh/g, and with the progress of a manufacturing process, the energy density of the lithium ion battery is gradually close to the theoretical value and cannot meet the energy storage requirement of rapid development, so that the design and research of the negative electrode material with high specific energy are a necessary way for realizing the high-energy-density battery. The lithium metal is adopted to replace graphite as the negative electrode of the battery, the theoretical specific capacity can be improved to 3860mAh/g, and meanwhile, the lithium metal negative electrode has extremely low standard electrode potential (-3.045V vs. SHE) and very small density (0.534 g/cm)3) And the cathode material is matched and assembled to obtain extremely high volume energy density. However, the purpose of high energy density can be achieved only when the thickness of the metallic lithium negative electrode in the battery is limited.
However, the lithium content in lithium metal batteries is usually more than ten times the actual circulating capacity, and assuming that all active lithium is involved in the reaction, the theoretical specific capacity of lithium metal is 3860mAh/g, and when the lithium is 10 times excessive, the actual theoretical capacity is reduced to 3860/(10+1) ═ 351mAh/g, which is only equivalent to graphite. The large lithium excess also causes practical problems at the surface of the negative electrode to be masked because the cycling stability is artificially enhanced, and at the same time, the excess lithium metal causes a decrease in the practical energy density and safety problems during the production process. Therefore, it is necessary to limit the excess of lithium metal in the battery. The lithium metal battery without the negative electrode is adopted, the negative electrode current collector is directly used as the negative electrode in the battery assembling process, no active substance exists, and lithium metal is directly deposited on the negative electrode current collector in the first charging process. Since no excess lithium is present, the volume of the battery is reduced and the energy density is increased. However, because of the high chemical activity of lithium, lithium dendrites are easily formed on the surface, the SEI film is punctured, the electrolyte is further consumed, and non-conductive dead lithium is formed. Because the content of lithium is limited, no additional lithium is supplemented in the circulation process, so that the circulation stability of the battery is poor. Therefore, formation of a stable solid electrolyte interphase interface film (SEI film), and inhibition of dendrite growth is an important step for improving the performance of a lithium metal battery. The electrolyte is a very critical component of a lithium metal battery, and the nucleation of lithium metal, the growth of dendrites, and the formation of an SEI film are all related to the selection of the electrolyte. By adding a small amount of electrolyte additives, the surface of the negative electrode is modified in situ in the battery to form a uniform and stable SEI film, so that the stability of the lithium negative electrode is improved. Because the content of the additive is generally very small, the introduction of the additive has very little influence on the viscosity, the ionic conductivity and the like of an electrolyte system, and therefore, the lithium negative electrode can be modified simply and efficiently.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide an electrolyte solution for a metal battery and a metal battery.
The present invention provides an electrolyte for a metal battery, having the characteristics comprising: the electrolyte additive is one or more of indium salt, tin salt, bismuth salt and germanium salt.
In the electrolyte for a metal battery provided by the present invention, there is also a feature that: wherein the electrolyte additive is (C)nH2n+1COO)- mXm+N is an integer of 0 to 9, Xm+Is In3+、Sn2+Or Bi3+Any one of them.
In the electrolyte for a metal battery provided by the present invention, there is also a feature that: wherein the electrolyte additive is stannous isooctanoate or bismuth isooctanoate.
In the electrolyte for a metal battery provided by the present invention, there is also a feature that: wherein, liquid electrolyte includes: an organic solvent and a lithium salt or a sodium salt dissolved in the organic solvent.
In the electrolyte for a metal battery provided by the present invention, there is also a feature that: wherein the content of the electrolyte additive in the electrolyte is 1-5 wt% based on 100% of the total mass of the electrolyte.
In the electrolyte for a metal battery provided by the present invention, there is also a feature in which the lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium bis (oxalato) borate (LiBOB), lithium tetrafluoroborate (LiBF)4) Lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI).
In the electrolyte for a metal battery provided by the present invention, there is also a feature in which the concentration of the lithium salt is 0.5mol/L to 2 mol/L.
The electrolyte solution for a metal battery according to the present invention is characterized in that the organic solvent is at least one of a carbonate solvent and an ether solvent. The carbonate solvent is ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate or fluoroethylene carbonate. The ether solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, 1, 3-dioxolane or tetrahydrofuran.
The invention provides a metal battery, which is any one of a lithium metal battery, a sodium metal battery, a lithium metal battery without a negative electrode and a sodium metal battery without a negative electrode, and is characterized by comprising the following components: a positive electrode, a separator, a negative electrode, and an electrolytic solution, wherein the electrolytic solution is the electrolytic solution for a metal battery according to any one of claims 1 to 5.
In the metal battery provided by the present invention, there is also provided a feature that: wherein, the negative electrode of the lithium metal battery is lithium metal.
In the metal battery provided by the present invention, there is also provided a feature that: the lithium metal battery is a non-negative electrode lithium metal battery, the negative electrode of the non-negative electrode lithium metal battery is a negative electrode current collector, and the electrolyte of the non-negative electrode lithium metal battery also contains lithium salt.
In the metal battery provided by the present invention, there is also provided a feature that: the positive electrode comprises a current collector and an active material layer on the current collector, the current collector is an aluminum foil, and the active material is any one of lithium iron phosphate, lithium cobaltate, lithium titanate, lithium manganate, nickel cobalt manganese ternary or nickel cobalt aluminum ternary.
In the metal battery provided by the present invention, there is also provided a feature that: wherein, the diaphragm is any one or more of a polypropylene diaphragm, a polyethylene diaphragm, a composite diaphragm of polypropylene and polyethylene, a glass fiber diaphragm, an alumina coating diaphragm or a polytetrafluoroethylene diaphragm.
Action and Effect of the invention
An electrolyte for a metal battery according to the present invention includes: the electrolyte additive is one or more of indium salt, tin salt, bismuth salt and germanium salt. Since metals such as indium, tin, and bismuth have a higher electrode potential than lithium, these metal ions can be reduced on the surface of the negative electrode by lithium, thereby forming an SEI film containing metal components in situ on the surface of the lithium negative electrode. In the circulation process, metal ions in the electrolyte have electrochemical activity, the stability of a metal protective layer on the surface of the lithium negative electrode is promoted, the metals can store lithium in an alloy forming mode, and meanwhile, the formed alloy can reduce a diffusion barrier in the lithium deposition process, promote the rapid migration of the lithium ions, inhibit the growth of lithium dendrites, and further improve the circulation stability of the lithium metal negative electrode.
Drawings
Fig. 1 is a graph showing charge and discharge curves of the 1 st, 100 th and 200 th circles at a 1C rate at room temperature for a lithium metal battery assembled according to test example 1 of the present invention using example 4 and comparative example 2;
fig. 2 is a graph of cycle performance at 1C rate of a lithium metal battery assembled by test example 1 using example 4 and comparative example 2 according to the present invention at room temperature;
fig. 3 is a graph showing charge and discharge curves at the 1 st, 2 nd, 3 rd and 10 th circles at a 0.1C rate at room temperature for a non-negative lithium metal battery assembled according to test example 2 of the present invention using example 7 and comparative example 3; and
fig. 4 is a graph showing cycle performance at 0.1C rate at room temperature of an assembled lithium metal battery without negative electrode of test example 2 according to the present invention using examples 5 to 7 and comparative example 3.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is specifically described below by combining the embodiment and the attached drawings.
< example 1>
Lithium ion battery electrolyte
The electrolyte consists of an organic solvent, lithium salt and an additive, wherein the organic solvent consists of ethylene carbonate and diethyl carbonate, the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1, the lithium salt is lithium hexafluorophosphate, the molar concentration of the lithium salt in the electrolyte is 1mol/L, the electrolyte additive is stannous isooctanoate, and the mass fraction in the electrolyte is 1 wt.%.
< example 2>
Lithium ion battery electrolyte
The electrolyte consists of an organic solvent, lithium salt and an additive, wherein the organic solvent consists of ethylene carbonate and diethyl carbonate, the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1, the lithium salt is lithium hexafluorophosphate, the molar concentration of the lithium salt in the electrolyte is 1mol/L, the electrolyte additive is stannous isooctanoate, and the mass fraction in the electrolyte is 2 wt.%.
< example 3>
Lithium ion battery electrolyte
The electrolyte consists of an organic solvent, lithium salt and an additive, wherein the organic solvent consists of ethylene carbonate and diethyl carbonate, the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1, the lithium salt is lithium hexafluorophosphate, the molar concentration of the lithium salt in the electrolyte is 1mol/L, the electrolyte additive is stannous isooctanoate, and the mass fraction in the electrolyte is 5 wt.%.
< comparative example 1>
Lithium ion battery electrolyte
The electrolyte consists of an organic solvent and lithium salt, wherein the organic solvent consists of ethylene carbonate and diethyl carbonate, the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1, the lithium salt is lithium hexafluorophosphate, and the molar concentration of the lithium salt in the electrolyte is 1 mol/L.
< example 4>
Preparation method of lithium metal battery
The preparation method of the lithium metal battery comprises the following steps:
preparation of the positive electrode: the ternary material (NCM523) is used as a positive electrode material, carbon black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, the three materials are uniformly mixed in N-methyl pyrrolidone (NMP) according to the mass ratio of 80:10:10, coated on an aluminum foil, dried, cut into 12mm round pieces, and dried in vacuum to obtain the positive electrode piece.
Assembling the lithium metal battery: the CR2025 button cell was assembled using the above positive electrode plate as the positive electrode, the lithium plate as the negative electrode, and the polypropylene (PP) as the separator, and using the electrolyte provided in example 3.
< comparative example 2>
Preparation method of lithium metal battery
The lithium metal battery was fabricated in the same manner as in example 4 except that the electrolyte provided in comparative example 1 was used in the assembly of the lithium metal battery.
< example 5>
Preparation method of lithium metal battery without negative electrode
The preparation method of the lithium metal battery without the negative electrode comprises the following steps:
preparation of the positive electrode: the ternary material (NCM523) is used as a positive electrode material, carbon black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, the three materials are uniformly mixed in N-methyl pyrrolidone (NMP) according to the mass ratio of 80:10:10, coated on an aluminum foil, dried, cut into 12mm round pieces, and dried in vacuum to obtain the positive electrode piece.
And (3) treatment of the negative electrode: and soaking the copper foil in 1mol/L hydrochloric acid solution for 10min, taking out, washing with deionized water and acetone respectively, vacuum drying, and transferring to a glove box to obtain the negative pole piece.
Assembling the lithium metal battery without the negative electrode: the positive electrode plate and the negative electrode plate are respectively used as a positive electrode and a negative electrode, polypropylene (PP) is used as a diaphragm, and the electrolyte provided in embodiment 1 is adopted to assemble the CR2025 button cell.
< example 6>
Preparation method of lithium metal battery without negative electrode
The preparation method of the lithium metal battery without negative electrode is the same as that of example 5, except that the electrolyte provided in example 2 is used in the assembly of the lithium metal battery without negative electrode.
< example 7>
Preparation method of lithium metal battery without negative electrode
The preparation method of the lithium metal battery without negative electrode is the same as that of example 5, except that the electrolyte provided in example 3 is used in the assembly of the lithium metal battery without negative electrode.
< comparative example 3>
Preparation method of lithium metal battery without negative electrode
The preparation method of the non-negative electrode lithium metal battery was the same as that of example 5 except that the electrolyte provided in comparative example 1 was used in the assembly of the non-negative electrode lithium metal battery.
< test example 1>
Electrochemical performance testing of lithium metal batteries
Electrochemical performance tests were performed on the assembled lithium metal batteries of example 4 and comparative example 2 using the novei test system.
The test method comprises the following steps: performing first-cycle charge-discharge activation at 25 deg.C under constant current of 0.1C, and then charging and discharging under constant current of 1C, wherein the charge-discharge voltage range is 3.0-4.3V.
The test results are shown in FIGS. 1-2. Fig. 1 is a graph showing charge and discharge curves of circles 1, 100 and 200 at a rate of 1C at room temperature for a lithium metal battery assembled according to test example 1 of the present invention using example 4 and comparative example 2. Fig. 2 is a graph showing cycle performance at room temperature at 1C rate of a lithium metal battery assembled according to test example 1 of the present invention using example 4 and comparative example 2.
As can be seen from fig. 1-2, the lithium metal battery assembled in example 4 has effectively improved cycle performance due to the addition of the electrolyte additive, and the capacity retention rate is about 81% after 300 cycles; the capacity of the lithium metal battery assembled by adopting the comparative example 2 is rapidly attenuated after 300 cycles, and the capacity retention rate of 300 cycles is only 30%, so that the cycle performance of the lithium metal battery can be effectively improved by adopting the electrolyte additive provided by the embodiment 4.
< test example 2>
Electrochemical performance testing of lithium metal batteries without negative electrode
Electrochemical performance tests were performed on the assembled lithium metal batteries without negative electrode of examples 5 to 7 and comparative example 3 using the novice test system.
The test method comprises the following steps: charging and discharging at 25 deg.C with constant current of 0.1C, and charging and discharging voltage range of 3.0-4.3V.
The test results are shown in fig. 3-4. Fig. 3 is a graph showing charge and discharge curves of circles 1, 2, 3 and 10 at a rate of 0.1C at room temperature for the lithium metal battery without negative electrode assembled in test example 2, example 7 and comparative example 3. Fig. 4 is a graph of cycle performance at 0.1C rate at room temperature for the assembled non-negative lithium metal batteries of test example 2 versus examples 5-7 and comparative example 3.
As can be seen from fig. 3 to 4, the cycle stability of the lithium metal battery without the negative electrode was significantly improved after the additive was added, and the capacity of the battery using comparative example 3 almost decayed to 0 after 40 cycles, whereas the retention rate of example 5 was 14%, the retention rate of example 6 was 29%, and the retention rate of the battery capacity of example 7 was 66%. Therefore, the cycle performance of the non-negative lithium metal battery can be significantly improved using the electrolyte additive provided in example 7.
Effects and effects of the embodiments
An electrolyte for a metal battery according to the present embodiment includes: the electrolyte additive is one or more of indium salt, tin salt, bismuth salt and germanium salt. Since metals such as indium, tin, and bismuth have a higher electrode potential than lithium, these metal ions can be reduced on the surface of the negative electrode by lithium, thereby forming an SEI film containing metal components in situ on the surface of the lithium negative electrode. In the circulation process, metal ions in the electrolyte have electrochemical activity, the stability of a metal protective layer on the surface of the lithium negative electrode is promoted, the metals can store lithium in an alloy forming mode, and meanwhile, the formed alloy can reduce a diffusion barrier in the lithium deposition process, promote the rapid migration of the lithium ions, inhibit the growth of lithium dendrites, and further improve the circulation stability of the lithium metal negative electrode.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. An electrolyte for a metal battery, comprising:
a liquid electrolyte and an electrolyte additive added to the liquid electrolyte,
wherein the electrolyte additive is one or more of indium salt, tin salt, bismuth salt and germanium salt.
2. The electrolyte for a metal battery according to claim 1, characterized in that:
wherein the electrolyte additive is (C)nH2n+1COO)- mXm+N is an integer of 0 to 9, Xm+Is In3+、Sn2+Or Bi3+Any one of them.
3. The electrolyte for a metal battery according to claim 1, characterized in that:
wherein the electrolyte additive is stannous isooctanoate or bismuth isooctanoate.
4. The electrolyte for a metal battery according to claim 1, characterized in that:
wherein the liquid electrolyte includes: an organic solvent and a lithium salt or a sodium salt dissolved in the organic solvent.
5. The electrolyte for a metal battery according to claim 1, characterized in that:
wherein the electrolyte additive is contained in the electrolyte in an amount of 1-5 wt.% based on 100% by mass of the total electrolyte.
6. A metal battery is any one of a lithium metal battery, a sodium metal battery, a non-negative sodium metal battery and a non-negative lithium metal battery, and is characterized by comprising: a positive electrode, a diaphragm, a negative electrode and an electrolyte,
wherein the electrolyte is the electrolyte for a metal battery according to any one of claims 1 to 5.
7. The metal battery of claim 6, wherein:
wherein the negative electrode of the lithium metal battery is lithium metal.
8. The metal battery of claim 6, wherein:
the lithium metal battery is a non-negative electrode lithium metal battery, the negative electrode of the non-negative electrode lithium metal battery is a negative electrode current collector, and the electrolyte of the non-negative electrode lithium metal battery also contains lithium salt.
9. The metal battery of claim 6, wherein:
the positive electrode comprises a current collector and an active material layer on the current collector, the current collector is an aluminum foil, and the active material is any one of lithium iron phosphate, lithium cobaltate, lithium titanate, lithium manganate, nickel cobalt manganese ternary or nickel cobalt aluminum ternary.
10. The metal battery of claim 5, wherein:
the diaphragm is any one or more of a polypropylene diaphragm, a polyethylene diaphragm, a polypropylene and polyethylene composite diaphragm, a glass fiber diaphragm, an alumina coating diaphragm or a polytetrafluoroethylene diaphragm.
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| CN113402353A (en) * | 2021-05-12 | 2021-09-17 | 华南理工大学 | Preparation and application of lithium metal negative electrode based on aromatized nitric acid free radical modification |
| CN114284553A (en) * | 2021-12-25 | 2022-04-05 | 西安交通大学 | Lithium metal battery without negative electrode and preparation method thereof |
| CN115411360A (en) * | 2021-05-26 | 2022-11-29 | 张家港市国泰华荣化工新材料有限公司 | Non-negative electrode lithium metal battery electrolyte and non-negative electrode lithium metal battery |
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Application publication date: 20210416 |