CN116154294A - Lithium ion battery and electricity utilization device - Google Patents
Lithium ion battery and electricity utilization device Download PDFInfo
- Publication number
- CN116154294A CN116154294A CN202310444172.7A CN202310444172A CN116154294A CN 116154294 A CN116154294 A CN 116154294A CN 202310444172 A CN202310444172 A CN 202310444172A CN 116154294 A CN116154294 A CN 116154294A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion battery
- sodium
- potassium
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 113
- 230000005611 electricity Effects 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 150000001768 cations Chemical class 0.000 claims abstract description 89
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 81
- 239000010439 graphite Substances 0.000 claims abstract description 81
- 239000003792 electrolyte Substances 0.000 claims abstract description 69
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 potassium tetrafluoroborate Chemical compound 0.000 claims description 57
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 20
- 239000011591 potassium Substances 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 19
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 9
- 159000000007 calcium salts Chemical class 0.000 claims description 9
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 claims description 3
- PWGVOCGNHYMDLS-UHFFFAOYSA-N 3-(2-methoxyethoxy)propan-1-amine Chemical compound COCCOCCCN PWGVOCGNHYMDLS-UHFFFAOYSA-N 0.000 claims description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 3
- MRSMFOBRKCROGJ-UHFFFAOYSA-L [Ca++].[O-]P(F)(F)=O.[O-]P(F)(F)=O Chemical compound [Ca++].[O-]P(F)(F)=O.[O-]P(F)(F)=O MRSMFOBRKCROGJ-UHFFFAOYSA-L 0.000 claims description 3
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- WKVRKSDUCURJNJ-UHFFFAOYSA-M potassium;difluorophosphinate Chemical compound [K+].[O-]P(F)(F)=O WKVRKSDUCURJNJ-UHFFFAOYSA-M 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims description 3
- FVCJARXRCUNQQS-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(O)=O FVCJARXRCUNQQS-UHFFFAOYSA-N 0.000 claims description 3
- KAEZJNCYNQVWRB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] KAEZJNCYNQVWRB-UHFFFAOYSA-K 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000009830 intercalation Methods 0.000 abstract description 8
- 230000002687 intercalation Effects 0.000 abstract description 8
- 239000011229 interlayer Substances 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 35
- 239000000463 material Substances 0.000 description 17
- 239000002131 composite material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
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- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- 241000289517 Colletotrichum lini Species 0.000 description 2
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- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
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Classifications
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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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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Abstract
The application provides a lithium ion battery and an electric device, wherein the lithium ion battery comprises a negative electrode plate and electrolyte; the negative electrode plate comprises graphite, the graphite comprises a lamellar structure, first cations are embedded between at least part of adjacent lamellar structures, and the electrolyte comprises the first cations, and the ionic radius of the first cations is larger than that of lithium ions. In the lithium ion preparation process, first cations are added into the electrolyte, and part of the first cations can be intercalated between adjacent sheets of graphite after formation, namely, in the finally prepared lithium ion battery, the negative electrode active material graphite and the electrolyte both contain the first cations; because the ionic radius of the first cation is larger than that of the lithium ion, the first cation intercalated into the graphite can prop open the interlayer spacing of the lamellar structure in the graphite, so that the subsequent lithium ion intercalation speed can be increased, the lithium precipitation on the surface of the negative electrode is reduced, the multiplying power performance of the negative electrode graphite is improved, and the quick charge performance of the lithium ion battery is improved.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a lithium ion battery and an electric device.
Background
The secondary battery has the outstanding characteristics of light weight, no pollution, no memory effect and the like, and is widely applied to various consumer electronic products and electric vehicles. Among them, lithium ion batteries are widely used in the fields of portable electronic devices, electric vehicles, and the like. With the development of the current society, the requirements of fast charging performance of lithium ion batteries are also increasing. However, in the related art, the lithium ion battery using graphite as the negative electrode active material has poor quick charge performance.
Therefore, improving the fast charge performance of lithium ion batteries employing graphite as the negative electrode active material is a problem that needs to be addressed.
Disclosure of Invention
Based on this, it is necessary to provide a lithium ion battery and an electric device to improve the quick charge performance of a lithium ion battery employing graphite as a negative electrode active material.
In order to achieve the above object, a first aspect of the present application provides a lithium ion battery, comprising:
the negative electrode plate comprises graphite, wherein the graphite comprises a lamellar structure, and first cations are embedded between at least part of adjacent lamellar layers; and
An electrolyte comprising the first cation;
The ionic radius of the first cation is larger than that of lithium ion; the maximum value of the spacing between the adjacent sheets is marked as d, and the maximum value of the spacing between the adjacent sheets meets the following conditions: d= 3.356 a+9.85 a×a, where a is the mass ratio of the first cation in the negative electrode sheet in the population formed by the first cation and the graphite.
In the lithium ion preparation process, first cations are added into the electrolyte, and part of the first cations can be intercalated between adjacent sheets of graphite after formation, namely, in the finally prepared lithium ion battery, the negative electrode active material graphite and the electrolyte both contain the first cations; because the ionic radius of the first cation is larger than that of the lithium ion, the first cation intercalated into the graphite can prop open the interlayer spacing of the lamellar structure in the graphite, so that the subsequent lithium ion intercalation speed can be increased, the lithium precipitation on the surface of the negative electrode is reduced, the multiplying power performance of the negative electrode graphite is improved, and the quick charge performance of the lithium ion battery is improved.
In some embodiments, 0% < a.ltoreq.10%.
In some embodiments, 0% < a.ltoreq.5%.
In some embodiments, 3.356A < d.ltoreq.4.341A.
In some embodiments, 3.356A < d.ltoreq. 3.849A.
In some embodiments, the concentration of the first cation contained in the electrolyte is 0.01mol/L to 0.3mol/L.
In some embodiments, the concentration of the first cation contained in the electrolyte is 0.05-0.3mol/L.
In some embodiments, the first cation comprises one or more of potassium ion, sodium ion, and calcium ion.
In some embodiments, the electrolyte includes a salt including the first cation, the salt including one or more of a potassium salt, a sodium salt, and a calcium salt.
In some embodiments, the potassium salt comprises one or more of potassium perchlorate, potassium tetrafluoroborate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium bistrifluoromethylsulfonimide, potassium difluorophosphate, potassium bistrifluorosulfonylimide, potassium bisoxalato borate, and potassium difluorooxalato borate.
In some embodiments, the potassium salt comprises one or more of potassium tetrafluoroborate, potassium hexafluorophosphate, potassium difluorosulfonimide, and potassium difluorooxalato borate.
In some embodiments, the sodium salt comprises one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium hexafluoroarsenate, sodium trifluoromethylsulfonimide, sodium difluorophosphate, sodium difluorosulfimide, sodium bisoxalato borate, and sodium difluorooxalato borate.
In some embodiments, the sodium salt comprises one or more of sodium tetrafluoroborate, sodium hexafluorophosphate, sodium difluorosulfonimide, and sodium difluorooxalato borate.
In some embodiments, the calcium salt comprises one or more of calcium perchlorate, calcium tetrafluoroborate, calcium hexafluoroarsenate, calcium trifluoromethylsulfonimide, and calcium difluorophosphate.
In some embodiments, the calcium salt comprises one or more of calcium tetrafluoroborate and calcium trifluoromethylsulfonimide.
In some embodiments, the ratio of the mass of the electrolyte to the nominal capacity of the lithium ion battery is 1g/Ah to 5g/Ah.
In some embodiments, the graphite comprises at least one of synthetic graphite and natural graphite.
In some embodiments, the electrolyte further comprises a lithium salt having at least one of the following characteristics:
(1) The lithium salt comprises one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorooxalate phosphate, lithium bis-fluorosulfonyl imide and lithium bis-trifluoromethanesulfonyl imide;
(2) The concentration of the lithium salt in the electrolyte is 0.5mol/L to 3mol/L.
In some embodiments, the concentration of the lithium salt in the electrolyte is 0.5mol/L to 1.5mol/L.
In some embodiments, the electrolyte further comprises an additive having at least one of the following characteristics:
(1) The additive comprises one or more of vinylene carbonate, vinyl ethylene carbonate, trimethylsilyl phosphate and fluoroethylene carbonate;
(2) The mass ratio of the additive in the electrolyte is less than or equal to 50 percent.
A second aspect of the present application provides an electrical device comprising a lithium ion battery of the first aspect of the present application.
Drawings
Fig. 1 is a schematic view of a lithium ion battery according to an embodiment of the present application.
Fig. 2 is an exploded view of the lithium ion battery of an embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic view of an electrical device for use as a power source for a lithium-ion battery according to an embodiment of the present application.
Reference numerals illustrate:
1 a lithium ion battery; 11 a housing; 12 electrode assembly; 13 cover plate; 2 an electric device.
Detailed Description
In order to facilitate an understanding of the present application, a more complete description of the present application will now be provided with reference to the relevant figures. Preferred embodiments of the present application are shown in the accompanying drawings. This application may, however, be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
In the present application, the technical features described in an open manner include a closed technical scheme composed of the listed features, and also include an open technical scheme including the listed features.
In the present application, reference is made to numerical intervals, where the numerical intervals are considered to be continuous unless specifically stated, and include the minimum and maximum values of the range, and each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
In this application, referring to units of data range, if a unit is only carried behind the right endpoint, the units representing the left endpoint and the right endpoint are the same. For example, 10-1000nm means that the units of "10" at the left end and "1000" at the right end are nm (nanometers).
The terms "plurality", "plural", and the like are used herein, and refer to a number of 2 or more, unless otherwise specified. For example, "plural" means two or more. Only a few numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. The scope of this definition may be inclusive or exclusive of the endpoints.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
With the development of society, the requirements of people on the quick charge performance of lithium ion batteries are higher and higher; however, in the related art, the lithium ion battery using graphite as the negative electrode active material has poor quick charge performance. The inventor of the application finds that, mainly because the mode of lithium storage of the graphite is intercalation, lithium ions are intercalated between sheets of the graphite, and because the graphite has two-dimensional diffusion characteristics and a smaller interlayer distance, the diffusion rate of the lithium ions between the sheets of the graphite has a certain limit. When the charge-discharge multiplying power is overlarge, the diffusion rate of lithium ions in the electrolyte is far greater than the diffusion rate of lithium ions between graphite sheets, a large amount of lithium ions are gathered on the surface of graphite, a large amount of ions gathered on the surface of graphite cannot be quickly diffused between the graphite sheets from the surface of graphite, a large amount of lithium ions are gathered on the surface of graphite, and then are directly deposited on the surface of graphite, so that the quick charge performance of the graphite cathode is poor finally.
Based on the problems, in the preparation process of the lithium ion battery, first cations with the ionic radius larger than that of lithium ions are added into the electrolyte, the first cations enter between adjacent sheets of negative graphite in the formation process, and finally the negative graphite of the prepared lithium ion battery and the electrolyte both contain the first cations; the first positive ions entering between the negative electrode graphite sheets can prop open the spacing between the graphite sheets, so that the speed of subsequent lithium ion intercalation is increased, the aggregation of lithium ions on the surface of the negative electrode graphite is reduced, the rate capability of the negative electrode graphite is improved, and the quick charge performance of a lithium ion battery is improved.
A first aspect of the present application provides a lithium ion battery comprising a negative electrode tab and an electrolyte; the negative electrode plate comprises graphite, the graphite comprises a lamellar structure, at least part of adjacent lamellar layers are embedded with first cations, the electrolyte comprises the first cations, and the ionic radius of the first cations is larger than that of lithium ions; the maximum value of the spacing between adjacent sheets is denoted as d, and the maximum value of the spacing between adjacent sheets satisfies: d= 3.356 a+9.85 a×a, where a is the mass ratio of the first cation in the negative electrode sheet in the population formed by the first cation and graphite.
It should be noted that the "first cation" and the like are used for descriptive purposes only, and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of the indicated technical feature.
The graphite has a lamellar structure, including multi-layered lamellae, and may have first cations embedded in the interstices between all adjacent lamellae, or may have first cations embedded in only some of the interstices between adjacent lamellae. In addition, after the first cations are intercalated between the graphite sheets, the sheets of graphite may be equally spaced or non-equally spaced. The maximum value of the spacing between adjacent sheets refers to the spacing between adjacent sheets that are separated by the greatest distance.
In the above-mentioned anode, the mass ratio of the first cation in the population formed by the first cation and graphite may be measured by inductively coupled plasma spectrometry.
The maximum value of the spacing between the adjacent graphite sheets can be obtained by testing by an X-ray diffraction method, and specifically comprises the following steps: discharging the battery cell to 2.5V, taking out the negative electrode plate after disassembly, soaking the negative electrode plate with dimethyl carbonate for three times, 15 minutes each time, and drying after cleaning. Placing the negative electrode plate in a Bruker D8 XRD diffractometer, and testing by adopting a Cu target; the test angle is 10-70 deg.. According to the angle 2 theta measured by XRD, calculating the graphite layer spacing d through a Bragg equation 2dsin theta=nλ; where n is the diffraction order and λ is the x-ray wavelength.
Understandably, by adding the first cations into the electrolyte during the preparation of lithium ions, part of the first cations after formation can be inserted between adjacent sheets of the negative electrode material graphite, namely, in the finally prepared lithium ion battery, the negative electrode active material graphite and the electrolyte both contain the first cations; because the ionic radius of the first cation is larger than that of the lithium ion, the first cation intercalated into the graphite can prop open the interlayer spacing of the lamellar structure in the graphite, so that the subsequent lithium ion intercalation speed can be increased, the lithium precipitation on the surface of the negative electrode is reduced, the multiplying power performance of the negative electrode graphite is improved, and the quick charge performance of the lithium ion battery is improved.
In some possible embodiments, 0% < a.ltoreq.10%; for example, it may be, but is not limited to, 0.01%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% or a range between any two of the foregoing values. In the negative electrode, when the mass ratio of the first cation in the whole formed by the first cation and graphite is in the range, the spacing between the graphite sheets can be spread to a proper size, so that the rapid intercalation and deintercalation of lithium ions are facilitated, and meanwhile, the instability of an SEI film caused by overlarge spacing between the sheets can be avoided. Optionally, 0% < a.ltoreq.5%.
As one possible embodiment, 3.356A < d.ltoreq.4.341A. For example, it may be, but is not limited to, 3.357 a, 3.4 a, 3.45 a, 3.5 a, 3.55 a, 3.6 a, 3.65 a, 3.7 a, 3.75 a, 3.8 a, 3.85 a, 3.9 a, 3.95 a, 4 a, 4.1 a, 4.15 a, 4.2 a, 4.25 a, 4.3 a, 4.341 a, or a range between any two of the foregoing values. When the maximum value of the interval between the adjacent sheets is in the range, the lithium ions can enter and exit between the sheets of the graphite, the speed of subsequent lithium ion intercalation is increased, the precipitation of the lithium ions on the surface of the negative electrode graphite is reduced, and the quick charge performance of the lithium ions is improved. Alternatively, 3.356A < d.ltoreq. 3.849A.
In some embodiments, the concentration of the first cation contained in the electrolyte is 0.01mol/L to 0.3mol/L; for example, it may be, but is not limited to, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, or a range between any two of the above. When the concentration of the first cation contained in the electrolyte is lower than the above range, the amount of the first cation which is intercalated between the graphite sheets at the time of formation may be small, and the spacing between the graphite sheets cannot be effectively increased; when the concentration of the first cations contained in the electrolyte is higher than the above range, a large amount of the first cations may be intercalated between the graphite sheets during formation, which may result in an excessively large spacing between the graphite sheets, thereby damaging the SEI film on the negative electrode surface and deteriorating the cycle performance of the lithium ion battery. Alternatively, the concentration of the first cation contained in the electrolyte is 0.05mol/L to 0.3mol/L.
The concentration of the first cation contained in the electrolyte refers to the concentration of the first cation remaining in the electrolyte of the lithium ion battery after formation.
The concentration of the first cation contained in the above-mentioned electrolyte may be measured using inductively coupled plasma emission spectrometry.
In some embodiments, the first cation comprises one or more of potassium, sodium, and calcium ions. The ionic radius of potassium ion, sodium ion and calcium ion is larger than that of lithium ion, and the potassium ion, the sodium ion and the calcium ion can be respectively embedded between graphite sheets, so that the lithium ion, the sodium ion and the calcium ion can be used as electrolyte to be added into electrolyte to prop open the interlayer of graphite after formation.
In some of these embodiments, the electrolyte includes a salt comprising a first cation, the salt comprising one or more of a potassium salt, a sodium salt, and a calcium salt.
Optionally, the potassium salt comprises one or more of potassium perchlorate, potassium tetrafluoroborate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium bistrifluoromethylsulfonylimide, potassium difluorophosphate, potassium bistrifluorosulfonylimide, potassium bisoxalato borate, and potassium difluorooxalato borate; further alternatively, the potassium salt comprises one or more of potassium tetrafluoroborate, potassium hexafluorophosphate, potassium difluorosulfonimide and potassium difluorooxalato borate.
Optionally, the sodium salt comprises one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium hexafluoroarsenate, sodium trifluoromethylsulfonimide, sodium difluorophosphate, sodium difluorosulfimide, sodium bisoxalato borate, and sodium difluorooxalato borate; further alternatively, the sodium salt comprises one or more of sodium tetrafluoroborate, sodium hexafluorophosphate, sodium difluorosulfonimide and sodium difluorooxalato borate.
Optionally, the calcium salt comprises one or more of calcium perchlorate, calcium tetrafluoroborate, calcium hexafluoroarsenate, calcium trifluoromethylsulfonimide, and calcium difluorophosphate; further alternatively, the calcium salt comprises one or more of calcium tetrafluoroborate and calcium trifluoromethylsulfonimide.
The type of the salt containing the first cation included in the above-mentioned electrolyte may be determined by the following method: drying the electrolyte, evaporating the solvent to obtain salt, determining the type of cations in the salt by adopting an inductively coupled plasma luminescence spectrometry, and performing infrared, raman and nuclear magnetic testing on the salt to determine the type of anions, thereby determining the type of the salt.
In some embodiments, the ratio of the mass of the electrolyte to the nominal capacity of the lithium ion battery is 1g/Ah to 5g/Ah; for example, it may be, but is not limited to, 1g/Ah, 1.5g/Ah, 2g/Ah, 2.5g/Ah, 3g/Ah, 3.5g/Ah, 4g/Ah, 4.5g/Ah, 5g/Ah, or a range between any two of the foregoing values. When the ratio of the mass of the electrolyte to the nominal capacity of the lithium ion battery is within the above range, the electrolyte can maintain the battery with good cycle performance without excessively increasing the capacity of the battery cell.
In some embodiments, the graphite comprises at least one of artificial graphite and natural graphite.
In some embodiments, the electrolyte further comprises a lithium salt. Alternatively, the lithium salt comprises lithium hexafluorophosphate (LiPF 6 ) Lithium difluorophosphate (LiPO) 2 F 2 ) One or more of lithium difluorooxalato phosphate (LiODFB), lithium difluorosulfonimide (LiFSI), and lithium bistrifluoromethanesulfonimide (LiTFSI).
Alternatively, the concentration of the lithium salt in the electrolyte is 0.5mol/L to 3mol/L; for example, it may be, but is not limited to, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, or a range between any two of the above. Alternatively, the concentration of the lithium salt in the electrolyte is 0.5mol/L to 1.5mol/L.
In some embodiments, the lithium salt may further include lithium tetrafluoroborate (LiBF 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) One or more of lithium triflate (LiTFS), lithium difluorooxalato borate (LiDFOB), lithium difluorooxalato borate (LiBOB), lithium difluorooxalato phosphate (LiDFOP), and lithium tetrafluorooxalato phosphate (LiTFOP).
In some possible embodiments, the electrolyte further comprises a solvent. Optionally, the solvent comprises one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, methyl acetate, ethyl propionate, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxolane, acetonitrile, dimethylacetamide, and dimethylsulfoxide.
When the first cation is sodium ion, one or more of tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxolane, acetonitrile, and dimethyl sulfoxide are preferably used as the solvent of the electrolyte. When the first cation is potassium ion, one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, methyl acetate, ethyl acetate and ethyl propionate are preferably used as the solvent of the electrolytic solution. When the first cation is calcium ion, one or more of tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxolane and dimethylacetamide are preferably used as the solvent of the electrolyte.
In some embodiments, the solvent may also be selected from one or more of fluoroethylene carbonate (FEC), dipropyl carbonate (DPC), methyl Propyl Carbonate (MPC), ethylene Propyl Carbonate (EPC), butylene Carbonate (BC), methyl Formate (MF), propyl Acetate (PA), methyl Propionate (MP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), sulfolane (SF), dimethylsulfone (MSM), methylsulfone (EMS), and diethylsulfone (ESE).
In some embodiments, the electrolyte further comprises an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
Optionally, the additive comprises one or more of vinylene carbonate, vinyl ethylene carbonate, trimethylsilyl phosphate, and fluoroethylene carbonate.
Optionally, the mass ratio of the additive in the electrolyte is less than or equal to 50%; for example, it may be, but is not limited to, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or a range between any two of the foregoing.
Typically, a lithium ion battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material on a polymeric material substrate. The metal material includes, but is not limited to, copper alloy, nickel alloy, titanium alloy, silver alloy, etc., and the polymer material substrate includes, but is not limited to, polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
In some embodiments, the negative active material may include a negative active material for a battery well known in the art, in addition to the graphite mentioned above. As an example, the anode active material may further include at least one of the following materials: soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more. The weight ratio of the negative electrode active material in the negative electrode film layer is 70-100% by weight based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS). The weight ratio of the binder in the negative electrode film layer is 0-30% by weight based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers. The weight ratio of the conductive agent in the negative electrode film layer is 0-20% by weight based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like. The weight ratio of the other auxiliary agents in the negative electrode film layer is 0-15% by weight based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components, in a solvent (such as deionized water) to form a negative electrode slurry, wherein the solid content of the negative electrode slurry is 30-70wt%, and the viscosity of the negative electrode slurry at room temperature is adjusted to 2000-10000 mPa.s; coating the obtained negative electrode slurry on the two side surfaces of a negative electrode current collector, performing a drying process, and cold pressing, such as a pair of rollers to obtain a negative electrode Pole pieces. The single-side coating unit area density of the negative electrode powder is 3-25 mg/cm 2 The compacted density of the negative electrode plate is 1.2-2.0 g/cm 3 。
Positive electrode plate
The positive pole piece comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector, wherein the positive film layer comprises the positive active material of the first aspect of the application.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material on a polymeric material substrate. Wherein the metal material includes, but is not limited to, aluminum alloy, nickel alloy, titanium alloy, silver alloy, and the like. The polymeric material substrate includes, but is not limited to, one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and Polyethylene (PE).
In some embodiments, the positive electrode active material may comprise a positive electrode active material for a battery as known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g. LiNiO) 2 ) Lithium manganese oxide (e.g. LiMnO 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxideLithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g. LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM) 333 ）、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM) 523 ）、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM) 211 ）、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM) 622 ）、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM) 811 ) Lithium nickel cobalt aluminum oxide (e.g. LiNi 0.85 Co 0.15 Al 0.05 O 2 ) And at least one of its modified compounds and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO 4 (also abbreviated as LFP)), composite material of lithium iron phosphate and carbon, and manganese lithium phosphate (such as LiMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, and a composite material of lithium manganese phosphate and carbon. The weight ratio of the positive electrode active material in the positive electrode film layer is 80-100% by weight based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin. The weight ratio of the binder in the positive electrode film layer is 0-20% by weight based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. The weight ratio of the conductive agent in the positive electrode film layer is 0-20% by weight based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the components for preparing the positive electrode plate, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methyl pyrrolidone) to form positive electrode slurry, wherein the solid content of the positive electrode slurry is 40-80wt%, the viscosity of the positive electrode slurry at room temperature is adjusted to 5000-25000 mPa.s, the positive electrode slurry is coated on the surfaces of both sides of a positive electrode current collector, and the positive electrode slurry is formed after being dried and cold-pressed by a cold rolling mill; the single-side coating unit area density of the positive electrode powder is 5-35 mg/cm 2 The compaction density of the positive pole piece is 1.5-4 g/cm 3 Optionally 2.0-3.6 g/cm 3 . The calculation formula of the compaction density is
Compacted density = coated area density/(post-extrusion pole piece thickness-current collector thickness).
Isolation film
In some embodiments, a separator is also included in the lithium ion battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability may be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the thickness of the separator is 4-40 μm, optionally 12-20 μm.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the lithium ion battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the lithium ion battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The lithium ion battery may also be packaged in a pouch, such as a pouch-type pouch. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the lithium ion battery is not particularly limited in this application, and may be cylindrical, square, or any other shape. For example, fig. 1 is a lithium ion battery 1 of a square structure as an example.
In some embodiments, referring to fig. 2, the overpack may include a housing 11 and a cover 13. The housing 11 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 11 has an opening communicating with the accommodation chamber, and the cover plate 13 can be provided to cover the opening to close the accommodation chamber.
The positive electrode sheet, the negative electrode sheet, and the separator may be formed into the electrode assembly 12 through a winding process or a lamination process. The electrode assembly 12 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 12. The number of electrode assemblies 12 included in the lithium ion battery 1 may be one or more, and may be adjusted according to the need.
In some embodiments, the lithium ion battery may be assembled into a battery module, and the number of secondary batteries included in the battery module may be plural, and the specific number may be adjusted according to the application and capacity of the battery module.
In the battery module, the plurality of secondary batteries may be sequentially arranged in the longitudinal direction of the battery module. Of course, the arrangement may be performed in any other way. The plurality of lithium ion batteries may further be secured by fasteners.
Alternatively, the battery module may further include a case having an accommodating space in which the plurality of lithium ion batteries are accommodated.
In some embodiments, the battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be adjusted according to the application and capacity of the battery pack.
A battery case and a plurality of battery modules disposed in the battery case may be included in the battery pack. The battery box comprises an upper box body and a lower box body, wherein the upper box body can be covered on the lower box body, and a closed space for accommodating the battery module is formed. The plurality of battery modules may be arranged in the battery case in any manner.
Power utilization device
A second aspect of the present application provides an electrical device comprising at least one of the lithium ion battery, the battery module or the battery pack of the first aspect of the present application. The lithium ion battery, battery module or battery pack may be used as a power source for the device, and may also be used as an energy storage unit for the device. The apparatus may be, but is not limited to, a mobile device, an electric vehicle, an electric train, a watercraft, a satellite, an energy storage system, and the like; wherein the mobile device may include, but is not limited to, at least one of a cell phone, a notebook computer, etc.; the electric vehicle may include, but is not limited to, at least one of a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf car, an electric truck, and the like.
The device may select a lithium ion battery, a battery module, or a battery pack according to its use requirements.
Fig. 3 is an electrical device 2 as an example. The electric device 2 is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. To meet the high power and high energy density requirements of the device for lithium ion batteries, a battery pack or battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a lithium ion battery can be used as a power supply.
The beneficial effects of the present application are further illustrated below in conjunction with the examples.
In order to make the technical problems, technical schemes and beneficial effects solved by the present application more clear, the following will be further described in detail with reference to the embodiments and the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the application, or its uses. All other embodiments, based on the embodiments herein, which are within the scope of the protection of the present application, will be within the skill of one of ordinary skill in the art without undue burden.
The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
1. Preparation of lithium ions
Example 1
1. Preparation of positive electrode plate
Mixing lithium iron phosphate (serving as an anode active material), polyvinylidene fluoride (PVDF) and conductive carbon black according to the proportion of 95:2:3, adding N-methylpyrrolidone, and stirring to prepare uniformly-dispersed slurry; uniformly coating the slurry on the surfaces of two sides of an aluminum foil, drying at 85 ℃, cold pressing, trimming and cutting, and drying for 4 hours under the vacuum condition at 85 ℃ to prepare the positive electrode plate.
2. Preparation of negative electrode plate
Mixing artificial graphite (serving as a negative electrode active material), carboxymethylcellulose lithium, styrene Butadiene Rubber (SBR) and conductive carbon black according to the proportion of 96:1.5:1.5, adding deionized water, stirring in vacuum to obtain uniform slurry, uniformly coating the slurry on the surfaces of two sides of a copper foil according to the designed weight, transferring the slurry into a vacuum drying oven, completely drying, and punching to obtain a negative electrode plate.
3. Preparation of electrolyte
LiPF is put into 6 (as lithium salt) and KPF 6 Dissolving (as salt containing first cation) in a mixture (as solvent) of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with volume ratio of 1:1, stirring uniformly to obtain LiPF 6 The concentration is 1mol/L, KPF 6 The concentration of the electrolyte is 0.3 mol/L.
4. Preparation of a separator film
A16 μm polyethylene film was used as a separator.
And stacking the positive electrode plate, the isolating film and the negative electrode plate in sequence to form a battery cell, enabling the isolating film to be positioned between the positive electrode plate and the negative electrode plate to play a role in isolating the positive electrode and the negative electrode plate, placing the bare battery cell in an outer package, injecting the prepared electrolyte into the dried battery cell, packaging, standing, slowly forming, and shaping to prepare the lithium ion battery.
Examples 2 to 15
The preparation methods of the lithium ion batteries in examples 2 to 15 are substantially the same as those of the lithium ion battery in example 1, and the main differences are that: at least one of the kind of the first cation, the kind of the salt containing the first cation, the mass of the first cation contained in the negative electrode sheet, the percentage of the first cation contained in the negative electrode sheet, the maximum value of the spacing between adjacent sheets, and the concentration of the first cation contained in the electrolyte is different. Details are shown in Table 1.
Comparative example 1
The difference between the preparation method of the lithium ion battery in comparative example 1 and the preparation method of the lithium ion battery in example 1 is that: the electrolyte is not added with KPF 6 。
The preparation parameters of each of the above examples and comparative examples are shown in Table 1, respectively.
TABLE 1
Wherein d represents the maximum value of the spacing between adjacent sheets of graphite, a represents the mass ratio of the first cation in the total formed by the first cation and graphite in the negative electrode sheet, m1 represents the concentration of the first cation contained in the electrolyte, and m2 represents the concentration of the salt containing the first cation in the electrolyte added when preparing the lithium ion battery; KPF (Key performance function) 6 Represents potassium hexafluorophosphate, liPF 6 Represents lithium hexafluorophosphate, BF4K represents potassium tetrafluoroborate, liPO 2 F 2 Represents lithium difluorophosphate, BF 4 Na represents sodium tetrafluoroborate, F 6 NaP represents sodium hexafluorophosphate.
Understandably, since the quality of the first cation embedded in the graphite cannot be precisely controlled, even though the embodiments in which the value of a is 5% and 10% respectively may not be given in the above embodiments, the value of a cannot be considered to be 5% and 10% in the technical solution of the present application; in contrast, the value of a in the technical scheme of the application can be unambiguously 5% and 10%.
The percentage of the mass of the first cation contained in the negative electrode sheet to the mass of the graphite contained in the negative electrode sheet mentioned in table 1 was measured by an inductively coupled plasma spectrometry.
The maximum value of the spacing between adjacent sheets of graphite mentioned in table 1 was determined by the following method: discharging the battery cell to 2.5V, taking out the negative electrode plate after disassembly, soaking the negative electrode plate with dimethyl carbonate for three times, 15 minutes each time, and drying after cleaning. Placing the negative electrode plate in a Bruker D8 XRD diffractometer, and testing by adopting a Cu target; the test angle is 10-70 deg.. According to the angle 2 theta measured by XRD, calculating the graphite layer spacing d through a Bragg equation 2dsin theta=nλ; where n is the diffraction order and λ is the x-ray wavelength.
The concentration of the first cation contained in the electrolyte mentioned in table 1 was measured by inductively coupled plasma emission spectrometry.
2. Performance testing
1. Rate capability test
Charging the battery cell to 3.65V, discharging to 2.5V, and circulating for 5 weeks at the current of 2C; then testing 5C current and 10C current multiplying power for 5 weeks by the same flow; the capacitance value at each current is recorded.
2. Cycle performance
Charging the cell to 3.65V with 0.5C current, and discharging to 2.5V with 0.5C current, and cycling for 200 weeks; the capacity retention ratio is a ratio of the discharge capacity per week to the discharge capacity of the first week.
The results of the performance tests of the above examples and comparative examples are shown in table 2 below.
TABLE 2
As can be seen from comparison of the results of examples 1 to 15 and comparative example 1 in Table 2, when preparing a lithium ion battery, by adding a first cation into an electrolyte, a part of the first cation after formation can be intercalated into a negative electrode material graphite, and the first cations with an ionic radius larger than that of lithium ions are contained between sheets of a negative electrode active material graphite of the finally prepared lithium ion battery and in the electrolyte, the interlayer spacing of a sheet structure in the graphite can be expanded, so that the rate of intercalation of subsequent lithium ions can be increased, and the rate performance and quick charge performance of the lithium ion battery can be improved.
Examples 1-8 differ mainly in that: in the negative electrode sheet, the first cations account for different mass ratios in the population formed by the first cations and graphite, and the maximum value of the spacing between adjacent sheets of graphite is different. The two parameter values were respectively maximum in example 8, and although example 8 had better rate performance, the 200-week cycle capacity retention rate was lower in example 8 than in examples 1 to 7, indicating that the cycle performance was poor in example 8. The reason for this is probably due to the fact that, when the mass ratio of the first cations in the total mass formed by the first cations and graphite in the negative electrode sheet is too large, the spacing between adjacent sheets of graphite is too large, and the SEI film on the surface of the negative electrode may be damaged, deteriorating the cycle performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples only represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the claims. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (20)
1. A lithium ion battery, comprising:
the negative electrode plate comprises graphite, wherein the graphite comprises a lamellar structure, and first cations are embedded between at least part of adjacent lamellar layers; and
An electrolyte comprising the first cation;
the ionic radius of the first cation is larger than that of lithium ion; the maximum value of the spacing between the adjacent sheets is marked as d, and the maximum value of the spacing between the adjacent sheets meets the following conditions: d= 3.356 a+9.85 a×a, where a is the mass ratio of the first cation in the negative electrode sheet in the population formed by the first cation and the graphite.
2. The lithium-ion battery of claim 1, wherein 0% < a ≡10%.
3. The lithium-ion battery of claim 2, wherein 0% < a ≡5%.
4. The lithium-ion battery of claim 1, wherein 3.356 a < d +.4.341 a.
5. The lithium-ion battery of claim 4, wherein 3.356 a < d.ltoreq. 3.849 a.
6. The lithium-ion battery of claim 1, wherein the concentration of the first cation contained in the electrolyte is 0.01 mol/L to 0.3 mol/L.
7. The lithium-ion battery of claim 6, wherein the concentration of the first cation contained in the electrolyte is 0.05-0.3 mol/L.
8. The lithium-ion battery of any of claims 1-7, wherein the first cation comprises one or more of potassium, sodium, and calcium ions.
9. The lithium-ion battery of claim 8, wherein the electrolyte comprises a salt comprising the first cation, the salt comprising the first cation comprising one or more of a potassium salt, a sodium salt, and a calcium salt.
10. The lithium ion battery of claim 9, wherein the potassium salt comprises one or more of potassium perchlorate, potassium tetrafluoroborate, potassium hexafluoroarsenate, potassium hexafluorophosphate, potassium bistrifluoromethylsulfonimide, potassium difluorophosphate, potassium bisfluorosulfonyl imide, potassium bisoxalato borate, and potassium difluorooxalato borate.
11. The lithium ion battery of claim 10, wherein the potassium salt comprises one or more of potassium tetrafluoroborate, potassium hexafluorophosphate, potassium difluorosulfonimide, and potassium difluorooxalato borate.
12. The lithium ion battery of claim 9, wherein the sodium salt comprises one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium hexafluoroarsenate, sodium trifluoromethylsulfonimide, sodium difluorophosphate, sodium difluorosulfimide, sodium bisoxalato borate, and sodium difluorooxalato borate.
13. The lithium-ion battery of claim 12, wherein the sodium salt comprises one or more of sodium tetrafluoroborate, sodium hexafluorophosphate, sodium difluorosulfonimide, and sodium difluorooxalato borate.
14. The lithium ion battery of any of claims 9 to 13, wherein the calcium salt comprises one or more of calcium perchlorate, calcium tetrafluoroborate, calcium hexafluoroarsenate, calcium trifluoromethylsulfonimide, and calcium difluorophosphate.
15. The lithium-ion battery of claim 14, wherein the calcium salt comprises one or more of calcium tetrafluoroborate and calcium trifluoromethylsulfonimide.
16. The lithium-ion battery according to any of claims 1-7 and 9-13, wherein the ratio of the mass of the electrolyte to the nominal capacity of the lithium-ion battery is 1g/Ah-5g/Ah.
17. The lithium-ion battery of any of claims 1-7 and 9-13, wherein the graphite comprises at least one of artificial graphite and natural graphite.
18. The lithium-ion battery of any of claims 1-7 and 9-13, wherein the electrolyte further comprises a lithium salt having at least one of the following characteristics:
(1) The lithium salt comprises one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorooxalate phosphate, lithium bis-fluorosulfonyl imide and lithium bis-trifluoromethanesulfonyl imide;
(2) The concentration of the lithium salt in the electrolyte is 0.5mol/L to 3mol/L.
19. The lithium-ion battery of any of claims 1-7 and 9-13, wherein the electrolyte further comprises an additive having at least one of the following characteristics:
(1) The additive comprises one or more of vinylene carbonate, vinyl ethylene carbonate, trimethylsilyl phosphate and fluoroethylene carbonate;
(2) The mass ratio of the additive in the electrolyte is less than or equal to 50 percent.
20. An electrical device comprising a lithium-ion battery as claimed in any one of claims 1 to 19.
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| WO2025000935A1 (en) * | 2023-06-28 | 2025-01-02 | 宁德时代新能源科技股份有限公司 | Battery cell and manufacturing method therefor, and battery and electric apparatus |
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