CN112615055A - Non-aqueous electrolyte and high-temperature-resistant lithium ion battery - Google Patents
Non-aqueous electrolyte and high-temperature-resistant lithium ion battery Download PDFInfo
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- CN112615055A CN112615055A CN202011521130.1A CN202011521130A CN112615055A CN 112615055 A CN112615055 A CN 112615055A CN 202011521130 A CN202011521130 A CN 202011521130A CN 112615055 A CN112615055 A CN 112615055A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- -1 methyl 2-propynyl carbonate Chemical compound 0.000 claims abstract description 29
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 25
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 10
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- FMUARYABUBCFKD-UHFFFAOYSA-N [amino(dimethylamino)methylidene]-dimethylazanium;trifluoromethanesulfonate Chemical compound CN(C)C(=N)N(C)C.OS(=O)(=O)C(F)(F)F FMUARYABUBCFKD-UHFFFAOYSA-N 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- 229960004198 guanidine Drugs 0.000 claims description 5
- LHFVAIZKWQDJJQ-UHFFFAOYSA-N (n,n-dimethylcarbamimidoyl)-dimethylazanium;2-hydroxypropanoate Chemical compound CC(O)C(O)=O.CN(C)C(=N)N(C)C LHFVAIZKWQDJJQ-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 3
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- GMGZEOLIKDSQTL-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine;hydrochloride Chemical compound [Cl-].CN(C)C(N)=[N+](C)C GMGZEOLIKDSQTL-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 21
- 229910001290 LiPF6 Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001323 Li2O2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910016133 LiNi1-x-y-zCoxMnyAlzO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a non-aqueous electrolyte and a high-temperature-resistant lithium ion battery, wherein the non-aqueous electrolyte comprises the following components: electrolyte lithium salt, tris (trimethylsilane) phosphate (TMSP), methyl 2-propynyl carbonate, citraconic anhydride, Propylene Carbonate (PC), and other solvents than propylene carbonate; wherein, C in the non-aqueous electrolyte2O6 2‑The concentration of (A) is 300ppm or less; SO (SO)4 2‑The concentration of (A) is 300ppm or less; li2O2The concentration of (B) is 100ppm or less. The non-aqueous electrolyte can improve the normal-temperature and high-temperature cycle performance of the lithium ion secondary battery, improve the high-temperature storage stability and inhibit high-temperature storage gas generation.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a non-aqueous electrolyte and a high-temperature-resistant lithium ion battery.
Background
In recent years, lithium secondary batteries have been widely used as power sources for small electronic devices such as mobile phones and notebook personal computers, and power sources for electric vehicles and power storage. Among these, laminated batteries or rectangular batteries using a laminate film such as an aluminum laminate film as an outer package member are often used in some thin electronic devices and some pure electric new energy vehicles, but these batteries are thin soft packages, and therefore, are prone to deformation such as swelling due to generation of gas inside the battery cell, which seriously affects normal operation of the electronic devices and modules.
In addition, the rate characteristics of the battery are gradually required to be improved in the new energy automobile market, and particularly, vehicles (such as PHEV and the like) which have requirements on rate performance have a lot of shares in the market, so that the battery is required to have lower impedance; the battery with good low impedance characteristic often has high gas production when stored at high temperature, and the high and low temperature performance can not be effectively considered. Generally, a method for improving the high temperature characteristics of the electrolyte is to add a high temperature additive to the electrolyte, which, however, results in poor normal temperature cycle characteristics of the battery.
Therefore, it is required to develop an electrolyte having a small gas production amount during high-temperature storage, a small DCR increase, and good stability and cyclability at high voltage.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a non-aqueous electrolyte and a high temperature resistant lithium ion battery, wherein the non-aqueous electrolyte of the present invention can improve normal temperature and high temperature cycle performance of a lithium ion secondary battery, improve high temperature storage stability, and inhibit high temperature storage gas generation.
The first purpose of the invention is to provide a nonaqueous electrolyte, which comprises the following components:
electrolyte lithium salt, tris (trimethylsilane) phosphate (TMSP), methyl 2-propynyl carbonate, citraconic anhydride, Propylene Carbonate (PC), and other solvents than propylene carbonate; wherein,
c in the nonaqueous electrolyte2O6 2-The concentration of (A) is 300ppm or less; SO (SO)4 2-The concentration of (A) is 300ppm or less; li2O2The concentration of (B) is 100ppm or less.
The non-aqueous electrolyte solution of the present inventionCitraconic anhydride and propylene carbonate are included, the citraconic anhydride contains unsaturated bonds and can be subjected to ring-opening polymerization, and the generation of organic gas is inhibited when a negative electrode is formed into a film; the PC as a solvent has the characteristics of high voltage resistance and stable chemical window, is helpful for high-temperature performance, and can improve the high-temperature storage stability of the electrolyte and inhibit high-temperature storage gas generation by matching the PC and the solvent; and C generated due to various side reactions is strictly controlled2O6 2-、SO4 2-And Li2O2The amount of (b) is such that the lithium ion secondary battery has better cycle performance after high-temperature storage.
Further, the structural formula of methyl 2-propynyl carbonate is as follows:
the 2-propynyl methyl carbonate is added into the non-aqueous electrolyte of the invention to be combined with other components, so that the normal temperature cycle performance and the high temperature storage performance of the electrolyte can be improved.
In the non-aqueous electrolyte, the tris (trimethylsilane) phosphate forms a CEI film on the surface of the positive electrode, has good lithium ion permeability, and can reduce impedance and improve rate characteristics.
Further, the content of each component in the nonaqueous electrolytic solution by weight is as follows:
10-20 parts of electrolyte lithium salt;
1-5 parts of tris (trimethylsilane) phosphate;
1-5 parts of 2-methyl propinyl carbonate;
5-10 parts of citraconic anhydride;
20-30 parts of propylene carbonate;
60-90 parts of other solvents except propylene carbonate.
Further, the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bis-fluorosulfonyl imide, lithium tetrafluoroborate and lithium perchlorate. Preferably, the electrolyte lithium salt comprises lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) And lithium perchlorate (LiClO)4)，LiBF4And LiClO4Each account for LiPF610-20% of the mole fraction.
Further, the other solvent is selected from a cyclic organic solvent or a linear organic solvent.
Further, the cyclic organic solvent is selected from one or more of ethylene carbonate and gamma-butyrolactone; the linear organic solvent is one or more selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate and propyl propionate.
Furthermore, the electrolyte also comprises 1-5 parts of ionic liquid containing guanidine cation.
Further, the ionic liquid containing guanidine cation is selected from one or more of guanidine hydrochloride, guanidine carbonate, tetramethyl guanidine lactate, tetramethyl guanidine hydrochloride and tetramethyl guanidine trifluoromethanesulfonate.
The ionic liquid has good conductivity, good stability and large specific heat capacity, is beneficial to improving the conductivity and high temperature resistance of the electrolyte, and the ionic liquid containing guanidine cations can effectively adsorb CO2And SO2The method is beneficial to reducing the impurity components in the electrolyte and inhibiting high-temperature storage gas generation.
The second purpose of the invention is to disclose the application of the non-aqueous electrolyte as the non-aqueous electrolyte of the high-temperature resistant lithium ion battery; the highest preservation temperature of the high-temperature resistant lithium ion battery is 65 ℃.
In the present invention, unless otherwise specified, "high temperature" means a temperature as high as 65 ℃.
Further, the lithium ion battery is a lithium secondary battery.
A third object of the present invention is to provide a lithium ion battery comprising a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a separator and an electrolyte disposed between the positive electrode and the negative electrode; the electrolyte solution includes the nonaqueous electrolyte solution of the present invention.
Further, the positive active material is selected from one or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium iron phosphate, lithium iron manganese phosphate, lithium nickel manganate, lithium cobalt manganate, lithium-rich manganese-based material and ternary positive materialSeveral, the structural formula of the ternary anode material is LiNi1-x-y-zCoxMnyAlzO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 1.
Further, the negative active material is selected from one or more of artificial graphite, natural graphite, silicon-oxygen compound, silicon-based alloy and active carbon.
Further, in the lithium ion battery, the type of the isolation film is not particularly limited, and may be selected according to actual requirements. Preferably, the diaphragm comprises a base film and a nano alumina coating coated on the base film, wherein the base film is at least one of PP, PE and PET, and the thickness of the nano alumina coating is 1.0-6.0 μm.
By the scheme, the invention at least has the following advantages:
the non-aqueous electrolyte disclosed by the invention controls the gas generation of the electrolyte when the electrolyte is stored at a high temperature (below 65 ℃) through the combination of various additives. Particularly, the high-temperature storage stability of the electrolyte is improved by the matching use of citraconic anhydride and propylene carbonate, and the high-temperature storage gas generation is inhibited; and C generated due to various side reactions is strictly controlled2O6 2-、SO4 2-And Li2O2The amount of (b) is such that the lithium ion secondary battery has better cycle performance after high-temperature storage.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following examples of the present invention, a method of manufacturing a lithium ion secondary battery is as follows:
LiNi as positive electrode active material0.5Co0.2Mn0.3O2(LNCM), conductive agent Keqin black, stickyThe binder polyvinylidene fluoride (PVDF) is fully stirred and uniformly mixed in an N-methyl pyrrolidone solvent system according to the mass ratio of 95: 3: 2, and then the mixture is coated on an aluminum foil to be dried and cold-pressed to obtain the positive pole piece, wherein the compaction density of the positive pole piece is 3.5g/cm3。
Fully stirring and uniformly mixing a negative active material graphite, a conductive agent Keqin black, a binder PVDF and a thickening agent sodium carboxymethyl cellulose (CMC) in a deionized water solvent system according to a mass ratio of 96: 2: 1, coating the mixture on a Cu foil, drying and cold pressing to obtain a negative pole piece, wherein the compaction density of the negative pole piece is 1.4g/cm3。
Polyethylene (PE) with the thickness of 9 mu m is taken as a base film, and a nano aluminum oxide coating layer with the thickness of 3 mu m is coated on the base film to obtain the diaphragm.
And stacking the positive pole piece, the diaphragm and the negative pole piece in sequence, so that the diaphragm is positioned between the positive pole piece and the negative pole piece to play an isolating role, and stacking the pieces to obtain the bare cell.
And (2) filling the bare cell into an aluminum plastic film, baking at 80 ℃ to remove water, injecting corresponding electrolyte, sealing, standing, hot-cold pressing, forming, clamping, capacity grading and other procedures to obtain the finished product of the flexibly-packaged lithium ion secondary battery.
Example 1
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF610 parts of LiBF42 parts of LiClO41 part, 1 part of TMSP, 1.2 parts of 2-propynyl methyl carbonate, 5.5 parts of citraconic anhydride, 22 parts of PC, 20 parts of ethylene carbonate, 20 parts of dimethyl carbonate and 20 parts of diethyl carbonate;
c in the nonaqueous electrolyte2O6 2-Is 280 ppm; SO (SO)4 2-Is 280 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Example 2
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF613 parts of LiBF42 portions of、LiClO41.5 parts, 2.5 parts of TMSP, 3 parts of 2-propynyl methyl carbonate, 7 parts of citraconic anhydride, 26 parts of PC, 20 parts of ethylene carbonate, 30 parts of dimethyl carbonate and 20 parts of propyl propionate;
c in the nonaqueous electrolyte2O6 2-Is 300 ppm; SO (SO)4 2-Has a concentration of 210 ppm; li2O2The concentration of (B) was 60 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Example 3
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF615 parts of LiBF41.5 parts of LiClO43 parts of TMSP4 parts, 4.5 parts of 2-propynyl methyl carbonate, 9 parts of citraconic anhydride, 30 parts of PC, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate and 20 parts of propyl propionate;
c in the nonaqueous electrolyte2O6 2-Has a concentration of 220 ppm; SO (SO)4 2-Has a concentration of 180 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Example 4
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF615 parts of LiBF41.5 parts of LiClO43 parts of TMSP4 parts, 4.5 parts of 2-propynyl methyl carbonate, 9 parts of citraconic anhydride, 30 parts of PC, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate, 20 parts of propyl propionate and 1.5 parts of tetramethyl guanidine trifluoromethanesulfonate;
c in the nonaqueous electrolyte2O6 2-Has a concentration of 220 ppm; SO (SO)4 2-Has a concentration of 180 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Example 5
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF615 parts of LiBF41.5 parts of LiClO43 parts, 4 parts of TMSP, 4.5 parts of 2-propynyl methyl carbonate, 9 parts of citraconic anhydride, 30 parts of PC, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate, 20 parts of propyl propionate, 1.5 parts of tetramethyl guanidine trifluoromethanesulfonate and 1.5 parts of tetramethyl guanidine lactate;
c in the nonaqueous electrolyte2O6 2-Has a concentration of 220 ppm; SO (SO)4 2-Has a concentration of 180 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Example 6
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF615 parts of LiBF41.5 parts of LiClO43 parts, 4 parts of TMSP, 4.5 parts of 2-propynyl methyl carbonate, 9 parts of citraconic anhydride, 30 parts of PC, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate, 20 parts of propyl propionate, 1.5 parts of tetramethyl guanidine trifluoromethanesulfonate, 1.5 parts of tetramethyl guanidine lactate and 1.5 parts of guanidine hydrochloride;
c in the nonaqueous electrolyte2O6 2-Has a concentration of 220 ppm; SO (SO)4 2-Has a concentration of 180 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Comparative example 1
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF68 parts of TMSP4 parts, 4.5 parts of 2-propynyl methyl carbonate, 30 parts of PC, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate and 20 parts of propyl propionate;
c in the nonaqueous electrolyte2O6 2-Has a concentration of 220 ppm; SO (SO)4 2-Has a concentration of 180 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Comparative example 2
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF68 parts of TMSP4 parts, 4.5 parts of 2-propynyl methyl carbonate, 9 parts of citraconic anhydride, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate and 20 parts of propyl propionate;
c in the nonaqueous electrolyte2O6 2-Has a concentration of 220 ppm; SO (SO)4 2-Has a concentration of 180 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Comparative example 3
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF610 parts of 2-propynyl methyl carbonate, 4.5 parts of citraconic anhydride, 5 parts of PC, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate and 20 parts of propyl propionate;
c in the nonaqueous electrolyte2O6 2-Has a concentration of 220 ppm; SO (SO)4 2-Has a concentration of 180 ppm; li2O2The concentration of (2) was 90 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
Comparative example 4
A nonaqueous electrolytic solution comprises the following components by weight:
LiPF610 parts of 2-propynyl methyl carbonate, 4.5 parts of citraconic anhydride, 2 parts of PC, 30 parts of ethylene carbonate, 35 parts of dimethyl carbonate and 20 parts of propyl propionate;
c in the nonaqueous electrolyte2O6 2-The concentration of (A) is 1000 ppm; SO (SO)4 2-Has a concentration of 1200 ppm; li2O2The concentration of (B) was 900 ppm.
The electrolyte is utilized to assemble the flexible package lithium ion secondary battery.
The above assembled different lithium ion secondary batteries were subjected to battery performance tests including
(1) Normal temperature (25 ℃) cycle life test
Placing the battery cell in a thermostat at 25 ℃ for cycle test, wherein the charging and discharging voltage interval is 2.8V-4.3V, and the charging and discharging multiplying power is 1C/1C; the capacity retention was determined after 1000cls was completed.
(2) High temperature (45 ℃) cycle life test
Placing the battery cell in a constant temperature box at 45 ℃ for cycle test, wherein the charging and discharging voltage interval is 2.8V-4.3V, and the charging and discharging multiplying power is 1C/1C; the capacity retention was determined after 1000cls was completed. (3) Volume expansion rate after high temperature storage (60 ℃)
The gas product volume change after high-temperature storage is as follows: charging the lithium secondary battery to 4.3V, and storing at 60 deg.C for 60 days; the volume of the lithium secondary battery was measured before and at the end of storage (test method was to calculate its buoyancy by putting into water and then its volume by archimedes' drainage method), and the change in volume after high-temperature storage of the battery was calculated as a percentage (volume after storage/initial volume-1) × 100%) based on before storage. The experiment was performed at 100% SOC.
As shown in Table 1, it can be seen that examples 1 to 6 have both low-temperature and high-temperature cycle stability and low volume expansion (gas production) after high-temperature storage.
TABLE 1 Performance test results for different batteries
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A non-aqueous electrolyte is characterized by comprising the following components:
electrolyte lithium salt, tris (trimethylsilane) phosphate, methyl 2-propynyl carbonate, citraconic anhydride, propylene carbonate, and other solvents than propylene carbonate; wherein,
c in the nonaqueous electrolyte2O6 2-The concentration of (A) is 300ppm or less; SO (SO)4 2-The concentration of (A) is 300ppm or less; li2O2The concentration of (B) is 100ppm or less.
2. The nonaqueous electrolytic solution of claim 1, wherein the contents of the components by weight are as follows:
10-20 parts of electrolyte lithium salt;
1-5 parts of tris (trimethylsilane) phosphate;
1-5 parts of 2-methyl propinyl carbonate;
5-10 parts of citraconic anhydride;
20-30 parts of propylene carbonate;
60-90 parts of other solvents except propylene carbonate.
3. The nonaqueous electrolytic solution of claim 1, wherein: the electrolyte lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bis-fluorosulfonyl imide, lithium tetrafluoroborate and lithium perchlorate.
4. The nonaqueous electrolytic solution of claim 1, wherein: the other solvent is selected from cyclic organic solvents or linear organic solvents.
5. The nonaqueous electrolytic solution of claim 4, wherein: the cyclic organic solvent is selected from one or more of ethylene carbonate and gamma-butyrolactone; the linear organic solvent is one or more selected from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate and propyl propionate.
6. The nonaqueous electrolytic solution of claim 1, wherein: the electrolyte also comprises 1-5 parts of ionic liquid containing guanidine cations.
7. The nonaqueous electrolytic solution of claim 6, wherein: the guanidine cation-containing ionic liquid is one or more selected from guanidine hydrochloride, guanidine carbonate, tetramethylguanidine lactate, tetramethylguanidine hydrochloride and tetramethylguanidine trifluoromethanesulfonate.
8. Use of the nonaqueous electrolytic solution of any one of claims 1 to 6 as a nonaqueous electrolytic solution for a high-temperature-resistant lithium ion battery; the maximum preservation temperature of the high-temperature resistant lithium ion battery is 65 ℃.
9. Use according to claim 8, characterized in that: the lithium ion battery is a lithium secondary battery.
10. A lithium ion battery, characterized by: the battery comprises a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, a diaphragm arranged between the positive electrode and the negative electrode and an electrolyte; the electrolyte includes the nonaqueous electrolyte solution described in any one of claims 1 to 6.
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