CN114204130B - Lithium ion battery and formation method and application thereof - Google Patents
Lithium ion battery and formation method and application thereof Download PDFInfo
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- CN114204130B CN114204130B CN202111493446.9A CN202111493446A CN114204130B CN 114204130 B CN114204130 B CN 114204130B CN 202111493446 A CN202111493446 A CN 202111493446A CN 114204130 B CN114204130 B CN 114204130B
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 180
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 97
- 238000002347 injection Methods 0.000 claims abstract description 97
- 239000007924 injection Substances 0.000 claims abstract description 97
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims description 74
- 239000002904 solvent Substances 0.000 claims description 53
- 239000000654 additive Substances 0.000 claims description 45
- 230000000996 additive effect Effects 0.000 claims description 45
- 229910003002 lithium salt Inorganic materials 0.000 claims description 39
- 159000000002 lithium salts Chemical class 0.000 claims description 39
- 238000007600 charging Methods 0.000 claims description 34
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 18
- 229910013872 LiPF Inorganic materials 0.000 claims description 17
- 101150058243 Lipf gene Proteins 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 229910012258 LiPO Inorganic materials 0.000 claims description 13
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 10
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- VXLCNTLWWUDBSO-UHFFFAOYSA-N Ethiazide Chemical compound ClC1=C(S(N)(=O)=O)C=C2S(=O)(=O)NC(CC)NC2=C1 VXLCNTLWWUDBSO-UHFFFAOYSA-N 0.000 claims 1
- 241001275899 Salta Species 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000243 solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000010277 constant-current charging Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
- 239000007787 solid Substances 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
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004804 winding Methods 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
- H01M10/052—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a lithium ion battery and a formation method and application thereof. The formation method comprises the following steps: performing primary injection on the non-formed lithium ion battery, and performing primary formation to complete the first-step formation; performing secondary liquid injection on the lithium ion battery after the first step of formation, and performing secondary formation to complete the second step of formation; and heating and standing the lithium ion battery after the second step of formation to finish formation of the lithium ion battery. According to the invention, the formation is completed in two steps, and the liquid injection is carried out before each step of formation, so that the water in the lithium ion battery is consumed by the formation process which is carried out immediately after the liquid injection, the water content in the lithium ion battery which is not easy to bake is reduced, a denser SEI film is formed, and the cycle life, the cycle performance and the safety performance of the lithium ion battery are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, relates to a formation method of a lithium ion battery, and in particular relates to a lithium ion battery, and a formation method and application thereof.
Background
The lithium ion battery is used as a novel formation power supply, has the characteristics of long cycle life, high energy density, high working voltage, no memory effect, environmental protection and the like, and is widely applied to various fields such as the fields of electronic products, electric automobiles, communication power supplies and the like.
In the lithium ion battery production process, formation is an important process in the lithium ion battery production process, and a passivation film, namely an SEI film, is formed on the surface of the negative electrode during formation. The quality of the SEI film directly influences the cycle performance, stability, self-discharge and other chemical properties of the lithium ion battery, and the SEI films formed by different formation processes are different, so that great differences exist in the performance of the lithium ion battery. At present, the quality problems of lithium ion battery bulge, low lithium ion battery capacity, short service life and the like easily occur in the industrial production process of the lithium ion battery. In the formation charging process, a small amount of water, hydrogen fluoride and an organic solvent in an electrolyte in the lithium ion battery can generate electrochemical reduction reaction to generate gas, and the gas causes the quality problems of swelling, poor appearance, low capacity and the like of the lithium ion battery. Therefore, moisture control is extremely important for lithium ion batteries, but for some nanoscale positive electrode materials, water is more easily absorbed than for micron-sized materials, and it is difficult to reduce the moisture to less than 100 ppm at the later stage of cell baking.
CN 105024098A discloses a lithium ion battery formation method, which belongs to the technical field of lithium ion battery preparation. The formation method comprises the following steps: step 1, after electrolyte is injected into a lithium ion battery, standing the lithium ion battery at room temperature for a first preset time; step 2, carrying out staged charging on the lithium ion battery obtained in the step 1 by using a first preset current, and measuring a first open-circuit voltage of the obtained lithium ion battery; step 3, standing the lithium ion battery obtained in the step 2 in an environment with preset pressure more than 0.1MPa for a third preset time, extracting gas in the obtained lithium ion battery, and measuring a second open-circuit voltage of the obtained lithium ion battery; and 4, comparing the difference value of the first open-circuit voltage and the second open-circuit voltage with a preset voltage, and circularly charging and discharging the lithium ion battery with the difference value of the first open-circuit voltage and the second open-circuit voltage smaller than the preset voltage by a second preset current.
CN 106785148A discloses a formation method and a lithium ion secondary battery, which are formed by four formation stages performed in sequence. The formation current of the four formation stages is gradually increased, and the negative pressure of four air extraction is linearly increased. The formation method can effectively improve the formation quality of the SEI film, reduce the swelling rate of the lithium ion battery, and further improve the comprehensive electrochemical performance of the lithium ion battery. The electrolyte of the lithium ion secondary battery is a nonaqueous system, and is subjected to a chemical conversion treatment by the chemical conversion method described above. The lithium ion secondary battery is not easy to bulge in the use process and has good comprehensive electrochemical performance.
The technical proposal improves the electrochemical performance of the lithium ion battery by improving the formation method, but the water absorption problem of the battery material can not be improved by the formation, so the problem of the cyclic gas production of the battery still exists.
How to improve the formation method and reduce the water absorption in the battery material is a technical problem to be solved in lithium ion batteries.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lithium ion battery and a formation method and application thereof, and the formation is completed in two steps, and liquid injection is carried out before each step of formation, so that the water in the lithium ion battery is consumed by the formation process immediately after liquid injection, the water content in the lithium ion battery, which is not easy to bake and dry, is reduced, a denser SEI film is formed, and the cycle life, the cycle performance and the safety performance of the lithium ion battery are improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a formation method of a lithium ion battery, the formation method comprising the steps of:
(1) Performing primary injection on the non-formed lithium ion battery, and performing primary formation to complete the first-step formation;
(2) Performing secondary liquid injection on the lithium ion battery after the first step of formation, and performing secondary formation to complete the second step of formation;
(3) And heating and standing the lithium ion battery after the second step of formation to finish formation of the lithium ion battery.
According to the invention, the formation is completed in two steps, and the liquid injection is carried out before each step of formation, so that the water in the lithium ion battery is consumed by the formation process which is carried out immediately after the liquid injection, the water content in the lithium ion battery which is not easy to bake is reduced, a denser SEI film is formed, and the coulomb efficiency, the cycle life and the safety performance of the lithium ion battery are improved.
Preferably, the primary injection in step (1) includes injecting a first electrolyte into the non-formed lithium ion battery.
Preferably, the first electrolyte includes a first lithium salt, a first additive, and a first solvent.
Preferably, the first lithium salt comprises LiPF with a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide, wherein the mass ratio is 1 (0.1-0.4), such as 1:0.1, 1:0.2, 1:0.25, 1:0.3 or 1:0.4, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the concentration of the first lithium salt in the first electrolyte is 1 to 1.5mol/L, for example, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L or 1.5mol/L, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the first additive comprises vinylene carbonate and/or fluoroethylene carbonate.
In the formation method provided by the invention, the additive contained in the electrolyte of the primary injection comprises vinylene carbonate and/or fluoroethylene carbonate, and the additive is favorable for forming a compact SEI film on the surface of the negative electrode due to low lithium ion migration speed under the conditions of low temperature and low current.
Preferably, the mass of the first additive in the first electrolyte is 1-3wt% of the first solvent, for example, 1wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the first solvent comprises ethylene carbonate.
Preferably, the time of the one injection in the step (1) is less than or equal to 1h, for example, 0.1h, 0.3h, 0.5h, 0.8h or 1h, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the temperature of the primary formation in step (1) is 5-15 ℃, for example, 5 ℃, 8 ℃, 10 ℃, 12 ℃ or 15 ℃, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the primary formation in step (1) is performed to 10-20% SOC, for example, 10% SOC, 12% SOC, 15% SOC, 16% SOC, 18% SOC, or 20% SOC, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the step of the primary formation in the step (1) is as follows: charging with constant current of 0.03-0.06C for 40-70min, standing for 5-15min, charging with constant current of 0.08-0.12C for 40-70min, and standing for 5-15min.
The constant current charging of 0.03 to 0.06C may be, for example, 0.03C, 0.04C, 0.05C, 0.055C or 0.06C, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The charging time is 40-70min, for example, 40min, 45min, 50min, 55min, 60min, 65min or 70min, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The time of the standing is 5-15min, for example, 5min, 8min, 10min, 12min or 15min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The constant current charging of 0.08-0.12C may be, for example, 0.08C, 0.09C, 0.1C, 0.11C or 0.12C, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention can consume the moisture which is not easy to bake in the pole piece well by small current formation immediately after the first liquid injection, and when the current is too large, a larger gas path is formed on the pole piece due to incomplete infiltration of the electrolyte, so that the performance is attenuated by shadow.
Preferably, the injecting in the step (2) includes injecting a second electrolyte into the lithium ion battery after the first step of formation.
Preferably, the second electrolyte comprises a second lithium salt, a second additive, and a second solvent.
Preferably, the second lithium salt comprises LiPF with a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide, wherein the mass ratio is 1 (0.1-0.4), such as 1:0.1, 1:0.2, 1:0.25, 1:0.3 or 1:0.4, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the concentration of the second lithium salt in the second electrolyte is 1 to 1.5mol/L, for example, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, or 1.5mol/L, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the second additive comprises lithium difluorodioxalate phosphate, tris (trimethylsilane) phosphite or LiPO 2 F 2 Any one or a combination of at least two of these. Typically but not by way of limitationThe combination of properties includes a combination of lithium difluorodioxalate phosphate and tris (trimethylsilane) phosphite, tris (trimethylsilane) phosphite and LiPO 2 F 2 Lithium difluorodioxalate phosphate and LiPO 2 F 2 Or lithium difluorodioxalate phosphate, tris (trimethylsilane) phosphite and LiPO 2 F 2 Is a combination of (a) and (b).
In the formation method provided by the invention, the additive in the second electrolyte of the secondary injection comprises lithium difluorobis (oxalato) phosphate, tris (trimethylsilane) phosphite or LiPO 2 F 2 Under the condition of high temperature and high current, the second electrolyte is decomposed and reformed at high temperature, so that the recombination of the negative electrode SEI film is facilitated, and the storage performance of the lithium ion battery cell is improved.
Preferably, the mass of the second additive in the second electrolyte is 1-3wt% of the second solvent, for example, 1wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the second solvent comprises dimethyl carbonate and/or diethyl carbonate.
Preferably, the time of the secondary injection in the step (2) is less than or equal to 1h, for example, 0.1h, 0.3h, 0.5h, 0.8h or 1h, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the injection coefficient of the sum of the two injection amounts of the primary injection and the secondary injection is 5.5-6g/Ah, for example, 5.5g/Ah, 5.6g/Ah, 5.7g/Ah, 5.8g/Ah, 5.9g/Ah or 6g/Ah, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the ratio of the injection amounts of the primary injection and the secondary injection is (65-75): (25-35), and for example, the ratio may be 65:35, 68:32, 70:30, 72:38 or 75:25, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
When the ratio of the liquid injection amount is larger than (65-75): 25-35, a larger air passage is formed on the pole piece due to the fact that the liquid injection amount is larger, so that capacity attenuation is quicker, and when the ratio of the liquid injection amount is smaller than (65-75): 25-35, formation effect is affected, and the moisture content of the pole piece cannot be well reduced.
Preferably, the temperature of the secondary formation in step (2) is 40-50 ℃, for example 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃ or 50 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the secondary formation in step (2) is performed to 30-50% SOC, for example, 30% SOC, 35% SOC, 40% SOC, 45% SOC, or 50% SOC, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the secondary forming in the step (2) includes: charging with constant current of 0.3-0.6C for 20-40min, and standing for 5-15min.
The constant current charging of 0.3 to 0.6C may be, for example, 0.3C, 0.4C, 0.5C, 0.55C or 0.6C, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The charging time is 20-40min, for example, 20min, 25min, 30min, 35min or 40min, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The time of the standing is 5-15min, for example, 5min, 8min, 10min, 12min or 15min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the heating in step (3) is 40-50 ℃, for example 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃ or 50 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the time of standing in the step (3) is 36-48h, for example, 36h, 38h, 40h, 42h, 44h, 46h or 48h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
As a preferred technical solution provided in the first aspect of the present invention, the formation method includes the following steps:
(1) Injecting the first electrolyte into the non-formed lithium ion battery, wherein the injection time is within 1h, performing primary formation to reach 10-20% SOC, charging the primary formation at 5-15 ℃ with constant current of 0.03-0.06C for 40-70min, standing for 5-15min, charging the primary formation with constant current of 0.08-0.12C for 40-70min, and standing for 5-15min to complete the first formation;
(2) Injecting a second electrolyte into the lithium ion battery after the first step of formation, wherein the injection time is within 1h, performing secondary formation to 30-50% SOC, charging the secondary formation at 40-50 ℃ with constant current of 0.3-0.6 ℃ for 20-40min, and standing for 5-15min to complete the second step of formation;
(3) Heating the lithium ion battery subjected to the second step to 40-50 ℃, and standing for 36-48h to finish the formation of the lithium ion battery;
the first electrolyte comprises a first lithium salt, a first additive and a first solvent; the first lithium salt comprises LiPF with a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1-1.5mol/L; the first additive comprises vinylene carbonate and/or fluoroethylene carbonate, and the mass of the first additive is 1-3wt% of that of the first solvent; the first solvent comprises ethylene carbonate;
the second electrolyte comprises a second lithium salt, a second additive and a second solvent; the second lithium salt comprises LiPF with a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1-1.5mol/L; the second additive comprises lithium difluorodioxalate phosphate, tris (trimethylsilane) phosphite or LiPO 2 F 2 Any one or a combination of at least two of the above, wherein the mass is 1-3wt% of the second solvent; the second solvent comprises dimethyl carbonate and/or diethyl carbonate.
In a second aspect, the present invention provides a lithium ion battery obtained according to the formation method of the first aspect.
In a third aspect, the present invention provides a use of the lithium ion battery according to the second aspect for an electric vehicle.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the invention, the formation is completed in two steps, and the liquid injection is carried out before each step of formation, so that the water in the lithium ion battery is consumed by the formation process which is carried out immediately after the liquid injection, the water content in the lithium ion battery which is not easy to bake is reduced, a denser SEI film is formed, and the cycle life, the cycle performance and the safety performance of the lithium ion battery are improved.
(2) The formation method provided by the invention effectively controls and reduces the moisture content in the positive plate, and is beneficial to forming an excellent SEI film, thereby reducing the possibility of further generating the SEI film in the battery circulation and storage process, reducing the consumption of the total amount of lithium in the battery, and improving the cycle life, the cycle performance and the safety performance of the battery.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
For reasons of space limitation, in order to compare the effects of the following examples and comparative examples providing technical solutions, the structure of the lithium ion battery according to the present invention, which is not formed as a lithium ion battery, is prepared by the following method:
(1) Preparation of a positive plate: NMP and PVDF are mixed and stirred at 25 ℃ to prepare positive electrode glue solution with 6% of solid content for standby; in a stirred tank, liFePO with the mass ratio of 95.5:1.8 is added 4 Stirring with SP for 60min; adding a certain amount of NMP into the stirring kettle, and stirring for 2 hours; adding a certain amount of CNT and PVDF glue solution into the slurry, wherein LiFePO 4 : CNT: the mass ratio of PVDF is 95.5:1:1.7, and the positive electrode slurry with the solid content of 53-55% is prepared after stirring for 3 hours; the positive electrode slurry is uniformly coated on a carbon-coated aluminum foil with the thickness of 14 mu m by adopting extrusion coating, and is dried at the temperature of 120 ℃ to prepare a dry positive electrode plate, wherein the single-sided area density of the positive electrode plate is 80g/m 2 。
(2) Preparing a negative plate: mixing CMC and deionized water in a stirring kettle at 25deg.C to obtain a mixture with a solid content of 1.5%Is used for later use; mixing and stirring graphite and SP in a mass ratio of 96:1.8 for 60min in another stirring kettle; adding a certain amount of CMC glue solution and water-based binder into a stirring kettle, and stirring for 120min, wherein CMC: the mass ratio of the aqueous binder is 0.4:1.8; adding a certain amount of deionized water into the negative electrode slurry, and stirring for 120min to finally prepare the negative electrode slurry with the solid content of 45-47%; the negative electrode slurry is uniformly coated on a carbon-coated copper foil with the thickness of 4.5 mu m by adopting extrusion coating, and is dried at the temperature of 90 ℃ to prepare a dry negative electrode plate, wherein the single-sided area density of the negative electrode plate is 60g/m 2 。
(3) Assembling a lithium ion battery: and winding the positive plate, the diaphragm and the negative plate to form a battery cell, welding lugs on two sides of the battery cell, placing the battery cell into an aluminum shell, welding a cover plate, and baking the battery cell in a baking oven at 100 ℃ for 24 hours to complete assembly. The diaphragm is a polyethylene diaphragm with the thickness of 12 mu m, the thickness of the lithium ion battery is 25mm, the width of the lithium ion battery is 100mm, the height of the lithium ion battery is 60mm, and the rated capacity of the lithium ion battery is 22Ah.
Example 1
The embodiment provides a formation method of a lithium ion battery, which comprises the following steps:
(1) Injecting the first electrolyte into the non-formed lithium ion battery, wherein the injection time is 0.5h, performing primary formation to 15% SOC, charging with constant current of 0.05C at 10 ℃ for 60min, standing for 10min, charging with constant current of 0.1C for 60min, and standing for 10min to complete the first formation;
(2) Injecting a second electrolyte into the lithium ion battery after the first step of formation, wherein the injection time is 0.5h, performing secondary formation to 40% SOC, charging the secondary formation at 45 ℃ with constant current of 0.5 ℃ for 30min, and standing for 10min to complete the second step of formation;
(3) Heating the lithium ion battery subjected to the second step to 45 ℃, and standing for 42h to finish the formation of the lithium ion battery;
the injection coefficient of the sum of the injection amounts of the injection solutions in the step (1) and the step (2) is 5.6g/Ah, and the ratio of the injection amounts of the first electrolyte to the second electrolyte is 7:3.
The first electrolyte comprises a first lithium salt, a first additive and a first solvent; the first lithium salt comprises LiPF with a mass ratio of 1:0.2 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.2mol/L; the first additive comprises 0.5wt% of vinylene carbonate and 1wt% of fluoroethylene carbonate by mass of a first solvent; the first solvent comprises ethylene carbonate;
the second electrolyte comprises a second lithium salt, a second additive and a second solvent; the second lithium salt comprises LiPF with a mass ratio of 1:0.2 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.2mol/L; the second additive is 0.5wt% of lithium difluorodioxalate phosphate, 0.4wt% of tris (trimethylsilane) phosphite and 0.3wt% of LiPO of the second solvent 2 F 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solvent is dimethyl carbonate and diethyl carbonate with a volume ratio of 4:3.
Example 2
The embodiment provides a formation method of a lithium ion battery, which comprises the following steps:
(1) Injecting the first electrolyte into the non-formed lithium ion battery, wherein the injection time is 0.8h, performing primary formation to 12% SOC, charging with constant current of 0.03C at 7 ℃ for 50min, standing for 5min, charging with constant current of 0.09C for 50min, and standing for 5min to complete the first formation;
(2) Injecting a second electrolyte into the lithium ion battery after the first step of formation for 0.8h, performing secondary formation to 35% SOC, charging the secondary formation at 42 ℃ with constant current of 0.4 ℃ for 25min, and standing for 5min to complete the second step of formation;
(3) Heating the lithium ion battery subjected to the second step to 42 ℃, and standing for 38 hours to finish the formation of the lithium ion battery;
the injection coefficient of the sum of the injection amounts of the injection solutions in the step (1) and the step (2) is 5.7g/Ah, and the ratio of the injection amounts of the first electrolyte to the second electrolyte is 68:32.
The first electrolyte comprisesA lithium salt, a first additive and a first solvent; the first lithium salt comprises LiPF with a mass ratio of 1:0.1 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.2mol/L; the first additive comprises 0.4wt% of vinylene carbonate and 1.1wt% of fluoroethylene carbonate by mass of a first solvent; the first solvent comprises ethylene carbonate;
the second electrolyte comprises a second lithium salt, a second additive and a second solvent; the second lithium salt comprises LiPF with a mass ratio of 1:0.1 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.2mol/L; the second additive is 0.6wt% of lithium difluorodioxalate phosphate, 0.5wt% of tris (trimethylsilane) phosphite and 0.4wt% of LiPO of the second solvent 2 F 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solvent is dimethyl carbonate and diethyl carbonate with a volume ratio of 5:4.
Example 3
The embodiment provides a formation method of a lithium ion battery, which comprises the following steps:
(1) Injecting the first electrolyte into the non-formed lithium ion battery, wherein the injection time is 0.9h, performing primary formation to 18% SOC, charging with constant current of 0.05C at 12 ℃ for 60min, standing for 10min, charging with constant current of 0.11C for 70min, and standing for 15min to complete the first formation;
(2) Injecting a second electrolyte into the lithium ion battery after the first step of formation, wherein the injection time is 0.9h, performing secondary formation to 45% SOC, charging the secondary formation at 48 ℃ with constant current of 0.5 ℃ for 35min, and standing for 10min to complete the second step of formation;
(3) Heating the lithium ion battery subjected to the second step to 48 ℃, and standing for 46h to finish the formation of the lithium ion battery;
the injection coefficient of the sum of the injection amounts of the injection solutions in the step (1) and the step (2) is 5.8g/Ah, and the ratio of the injection amounts of the first electrolyte to the second electrolyte is 72:38.
The first electrolyte comprises a first lithium salt, a first additive and a first solvent; the first lithium salt comprises the components in a mass ratio of 1:0.3LiPF 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.4mol/L; the first additive comprises 0.6wt% of vinylene carbonate and 1.2wt% of fluoroethylene carbonate by mass of a first solvent; the first solvent comprises ethylene carbonate;
the second electrolyte comprises a second lithium salt, a second additive and a second solvent; the second lithium salt comprises LiPF with a mass ratio of 1:0.3 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.4mol/L; the second additive is 0.7wt% of lithium difluorodioxalate phosphate, 0.6wt% of tris (trimethylsilane) phosphite and 0.5wt% of LiPO of the second solvent 2 F 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solvent is dimethyl carbonate and diethyl carbonate with a volume ratio of 3:2.
Example 4
The embodiment provides a formation method of a lithium ion battery, which comprises the following steps:
(1) Injecting the first electrolyte into the non-formed lithium ion battery, wherein the injection time is 0.3h, performing primary formation to 10% SOC, charging with constant current of 0.05C at the temperature of 5 ℃ for 40min, standing for 10min, charging with constant current of 0.08C for 40min, and standing for 10min to complete the first formation;
(2) Injecting a second electrolyte into the lithium ion battery after the first step of formation, wherein the injection time is 0.3h, performing secondary formation to 30% SOC, charging the secondary formation at 40 ℃ with constant current of 0.3 ℃ for 20min, and standing for 10min to complete the second step of formation;
(3) Heating the lithium ion battery subjected to the second step to 40 ℃, and standing for 36h to finish the formation of the lithium ion battery;
the injection coefficient of the sum of the injection amounts of the injection solutions in the step (1) and the step (2) is 5.5g/Ah, and the ratio of the injection amounts of the first electrolyte to the second electrolyte is 65:35.
The first electrolyte comprises a first lithium salt, a first additive and a first solvent; the first lithium salt comprises LiPF with a mass ratio of 1:0.2 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1mol/L; the first additive comprises a substanceVinylene carbonate and fluoroethylene carbonate in an amount of 0.5wt% and 0.5wt% of the first solvent; the first solvent comprises ethylene carbonate;
the second electrolyte comprises a second lithium salt, a second additive and a second solvent; the second lithium salt comprises LiPF with a mass ratio of 1:0.2 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1mol/L; the second additive is 0.5wt% of lithium difluorodioxalate phosphate, 0.3wt% of tris (trimethylsilane) phosphite and 0.2wt% of LiPO of the second solvent 2 F 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solvent is dimethyl carbonate and diethyl carbonate with a volume ratio of 4:3.
Example 5
The embodiment provides a formation method of a lithium ion battery, which comprises the following steps:
(1) Injecting a first electrolyte into the non-formed lithium ion battery for 1h, performing primary formation to 20% SOC, charging with a constant current of 0.06C at 15 ℃ for 70min, standing for 15min, charging with a constant current of 0.12C for 70min, and standing for 15min to complete the first formation;
(2) Injecting a second electrolyte into the lithium ion battery after the first step of formation for 1h, performing secondary formation to 50% of SOC, charging the secondary formation at 50 ℃ with constant current of 0.6 ℃ for 40min, and standing for 15min to complete the second step of formation;
(3) Heating the lithium ion battery subjected to the second step to 50 ℃, and standing for 48 hours to finish the formation of the lithium ion battery;
the injection coefficient of the sum of the injection amounts of the injection solutions in the step (1) and the step (2) is 6g/Ah, and the ratio of the injection amounts of the first electrolyte to the second electrolyte is 75:25.
The first electrolyte comprises a first lithium salt, a first additive and a first solvent; the first lithium salt comprises LiPF with a mass ratio of 1:0.4 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.5mol/L; the first additive comprises 1wt% of vinylene carbonate and 2wt% of fluoroethylene carbonate by mass of a first solvent; the first solventIncluding ethylene carbonate;
the second electrolyte comprises a second lithium salt, a second additive and a second solvent; the second lithium salt comprises LiPF with a mass ratio of 1:0.4 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1.5mol/L; the second additive is 1.5wt% of lithium difluorodioxalate phosphate, 0.8wt% of tris (trimethylsilane) phosphite and 0.7wt% of LiPO of the second solvent 2 F 2 The method comprises the steps of carrying out a first treatment on the surface of the The second solvent is dimethyl carbonate and diethyl carbonate with a volume ratio of 4:3.
Example 6
The present embodiment provides a formation method of a lithium ion battery, and the other process steps are the same as those of embodiment 1 except that the temperature condition of the primary formation in the step (1) is 20 ℃.
Example 7
The present embodiment provides a formation method of a lithium ion battery, and the other process steps are the same as those of embodiment 1 except that the temperature condition of the primary formation in the step (1) is 3 ℃.
Example 8
The embodiment provides a formation method of a lithium ion battery, and the rest of the process steps are the same as those of embodiment 1 except that the twice constant current charging of the primary formation in the step (1) are respectively 0.1C and 0.2C.
Example 9
The embodiment provides a formation method of a lithium ion battery, and the rest of the process steps are the same as those of embodiment 1 except that the twice constant current charging of the primary formation in the step (1) are respectively 0.01C and 0.05C.
Example 10
The present embodiment provides a formation method of a lithium ion battery, and the other process steps are the same as those of embodiment 1, except that the first electrolyte in step (1) is replaced with a second electrolyte of equal mass.
Example 11
The present embodiment provides a formation method of a lithium ion battery, and the other process steps are the same as those of embodiment 1, except that the second electrolyte in step (2) is replaced with the first electrolyte of equal mass.
Example 12
The present example provides a method for forming a lithium ion battery, and the process steps are the same as those of example 1 except that the temperature condition for the secondary formation in step (2) is 35 ℃.
Example 13
The present example provides a method for forming a lithium ion battery, and the process steps are the same as those of example 1 except that the temperature condition for the secondary formation in step (2) is 55 ℃.
Example 14
The present example provides a formation method of a lithium ion battery, and the other process steps are the same as those of example 1, except that the injection coefficient of the sum of the two injection amounts is 5.3 g/Ah.
Example 15
The present example provides a method for forming a lithium ion battery, and the process steps are the same as those of example 1, except that the injection coefficient of the sum of the two injection amounts is 6.2 g/Ah.
Example 16
The present embodiment provides a formation method of a lithium ion battery, and the other process steps are the same as those of embodiment 1, except that the ratio of the liquid injection amounts of the first electrolyte and the second electrolyte is 6:4.
Example 17
The present embodiment provides a formation method of a lithium ion battery, and the other process steps are the same as those of embodiment 1, except that the ratio of the liquid injection amounts of the first electrolyte and the second electrolyte is 8:2.
Comparative example 1
The comparative example provides a formation method of a lithium ion battery, the method is a conventional formation method, and the formation method comprises the following steps:
(1) Injecting electrolyte into the non-formed lithium ion battery at 25 ℃, and standing for 12 hours to finish the injection;
(2) And (3) charging the lithium ion battery after liquid injection under the constant current of 0.5C for 48min, wherein the cut-off voltage is 3.65V, and standing for 10min after the charging is finished, thus completing the formation.
The lithium ion batteries of examples 1 to 17 and comparative example 1 were tested at 150℃using a Karl Fischer moisture tester; the capacity retention after 1000cycles at 25℃at 1C/1C is shown in Table 1.
TABLE 1
From table 1, the following conclusions can be drawn:
(1) According to the embodiment 1-5, the formation is completed in two steps, and the liquid injection is carried out before each step of formation, so that the water in the lithium ion battery is consumed by the formation process carried out immediately after the liquid injection, the water content in the lithium ion battery, which is not easy to bake and dry, is reduced, a denser SEI film is formed, and the cycle life, the cycle performance and the safety performance of the lithium ion battery are improved.
(2) As can be seen from comparison of examples 6 and 7 with example 1, when the temperature of the primary formation exceeds 15 ℃ or is less than 3 ℃, the reduction of the moisture content of the positive electrode of the lithium ion battery after formation is small and the circulation is poor, which indicates that the temperature of the primary formation provided by the invention is favorable for reducing the moisture in the positive electrode sheet in the formation process, so that the lithium ion battery forms a denser SEI film and the cycle life, the cycle performance and the safety performance of the lithium ion battery are improved.
(3) As can be seen from comparison of examples 8 and 9 with example 1, when the two-step constant current charging current of one-time formation exceeds 0.03-0.06C and 0.08-0.12C, respectively, the reduction of the water content of the positive electrode of the lithium ion battery after formation is small and the circulation is poor, which indicates that the two-step constant current charging current of one-time formation provided by the invention is beneficial to reducing the water content in the positive electrode sheet in the formation process, thereby enabling the lithium ion battery to form a denser SEI film and improving the cycle life, the cycle performance and the safety performance of the lithium ion battery.
(4) As can be seen from the comparison between examples 10 and 11 and example 1, when the electrolyte of the first injection is the second electrolyte or the second injection is the first electrolyte, the reduction of the water content of the positive electrode of the lithium ion battery after formation is small and the circulation is poor, which indicates that the electrolyte of the second injection provided by the invention is beneficial to reducing the water content in the positive electrode sheet in the formation process, thereby enabling the lithium ion battery to form a denser SEI film and improving the cycle life, the cycle performance and the safety performance of the lithium ion battery.
(5) As can be seen from comparison of examples 12 and 13 with example 1, when the secondary formation temperature exceeds 50 ℃ or is less than 40 ℃, the reduction of the moisture content of the positive electrode of the lithium ion battery after formation is small and the circulation is poor, which indicates that the secondary formation temperature provided by the invention is favorable for reducing the moisture in the positive electrode sheet in the formation process, so that the lithium ion battery forms a denser SEI film, and the cycle life, the circulation performance and the safety performance of the lithium ion battery are improved.
(6) As can be seen from the comparison of examples 14 and 15 with example 1, when the injection coefficient of the sum of the two injection amounts is greater than 6g/Ah or less than 5.5g/Ah, the reduction of the water content of the positive electrode of the lithium ion battery after formation is not large and the circulation is poor, which indicates that the injection coefficient of the sum of the two injection amounts provided by the invention is favorable for reducing the water content in the positive electrode sheet in the formation process, thereby enabling the lithium ion battery to form a denser SEI film and improving the cycle life, the circulation performance and the safety performance of the lithium ion battery.
(7) As can be seen from the comparison of examples 16 and 17 with example 1, when the ratio of the liquid injection amounts of the primary liquid injection and the secondary liquid injection is not within the range of (65-75): 25-35, the reduction of the water content of the positive electrode of the lithium ion battery after formation is small in amplitude and poor in circulation, which indicates that the ratio of the liquid injection amounts of the primary liquid injection and the secondary liquid injection provided by the invention is beneficial to reducing the water content in the positive electrode sheet in the formation process, thereby enabling the lithium ion battery to form a denser SEI film and improving the cycle life, the cycle performance and the safety performance of the lithium ion battery.
(8) As can be seen from comparison of comparative example 1 and example 1, the present invention, unlike the conventional formation method, performs the formation in two steps, and performs the liquid injection before each step of formation, so that the water in the lithium ion battery is consumed by the formation process immediately after the liquid injection, and the water content in the lithium ion battery, which is not easy to bake to dryness, is reduced, thereby forming a denser SEI film, and improving the cycle life, cycle performance and safety performance of the lithium ion battery.
The detailed process flow of the present invention is described by the above embodiments, but the present invention is not limited to the above detailed process flow, i.e., it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (14)
1. The formation method of the lithium ion battery is characterized by comprising the following steps of:
(1) Injecting liquid into the non-formed lithium ion battery once, and performing primary formation until the SOC reaches 10-20%, so as to complete the first formation; the process of the one-step formation comprises the following steps: charging with constant current of 0.03-0.06C for 40-70min, standing for 5-15min, charging with constant current of 0.08-0.12C for 40-70min, and standing for 5-15min; the temperature of the primary formation is 5-15 ℃;
the primary injection comprises injecting a first electrolyte into the non-formed lithium ion battery; the first electrolyte comprises a first lithium salt, a first additive and a first solvent; the first additive comprises vinylene carbonate and/or fluoroethylene carbonate; the first solvent comprises ethylene carbonate;
(2) Performing secondary injection on the lithium ion battery after the first step of formation, and performing secondary formation until the SOC reaches 30-50%, so as to finish the second step of formation; the secondary formation process comprises the following steps: charging with constant current of 0.3-0.6C for 20-40min, and standing for 5-15min; the temperature of the secondary formation is 40-50 ℃;
the secondary injection comprises injecting a second electrolyte into the lithium ion battery after the first step of formation; the second electrolyte includes a second lithium saltA second additive and a second solvent; the second additive comprises lithium difluorodioxalate phosphate, tris (trimethylsilane) phosphite or LiPO 2 F 2 Any one or a combination of at least two of the following; the second solvent comprises dimethyl carbonate and/or diethyl carbonate;
(3) Heating and standing the lithium ion battery subjected to the second step of formation to finish formation of the lithium ion battery;
wherein the injection coefficient of the sum of the two injection amounts of the primary injection and the secondary injection is 5.5-6g/Ah; the ratio of the liquid injection amount of the primary liquid injection to the liquid injection amount of the secondary liquid injection is (65-75): 25-35.
2. The method according to claim 1, wherein the first lithium salt comprises LiPF having a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide.
3. The method of claim 1, wherein the concentration of the first lithium salt in the first electrolyte is 1-1.5mol/L.
4. The method according to claim 1, wherein the mass of the first additive in the first electrolyte is 1-3wt% of the first solvent.
5. The method according to claim 1, wherein the time of the one injection in the step (1) is not more than 1 hour.
6. The chemical conversion method according to claim 1, wherein the time of the secondary injection in the step (2) is not more than 1 hour.
7. The method according to claim 1, wherein the second lithium salt comprises LiPF having a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide.
8. The method of claim 1, wherein the concentration of the second lithium salt in the second electrolyte is 1-1.5mol/L.
9. The method according to claim 1, wherein the mass of the second additive in the second electrolyte is 1-3wt% of the second solvent.
10. The method of claim 1, wherein the elevated temperature in step (3) is 40-50 ℃.
11. The method of claim 1, wherein the time of standing in step (3) is 36-48 hours.
12. The method of forming according to claim 1, characterized in that the method of forming comprises the steps of:
(1) Injecting the first electrolyte into the non-formed lithium ion battery, wherein the injection time is within 1h, performing primary formation to reach 10-20% SOC, charging the primary formation at 5-15 ℃ with constant current of 0.03-0.06C for 40-70min, standing for 5-15min, charging the primary formation with constant current of 0.08-0.12C for 40-70min, and standing for 5-15min to complete the first formation;
(2) Injecting a second electrolyte into the lithium ion battery after the first step of formation, wherein the injection time is within 1h, performing secondary formation to 30-50% SOC, charging the secondary formation at 40-50 ℃ with constant current of 0.3-0.6 ℃ for 20-40min, and standing for 5-15min to complete the second step of formation;
(3) Heating the lithium ion battery subjected to the second step to 40-50 ℃, and standing for 36-48h to finish the formation of the lithium ion battery;
the first electrolyte comprises a first lithium salt, a first additive and a first solvent; the first lithium salt comprises LiPF with a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1-1.5mol/L; the first additive comprises vinylene carbonate and/or fluoroethylene carbonate, and the mass of the first additive is 1-3wt% of that of the first solvent; the first solventAgents include ethylene carbonate;
the second electrolyte comprises a second lithium salt, a second additive and a second solvent; the second lithium salt comprises LiPF with a mass ratio of 1 (0.1-0.4) 6 And lithium bis (fluorosulfonyl) imide at a concentration of 1-1.5mol/L; the second additive comprises lithium difluorodioxalate phosphate, tris (trimethylsilane) phosphite or LiPO 2 F 2 Any one or a combination of at least two of the above, wherein the mass is 1-3wt% of the second solvent; the second solvent comprises dimethyl carbonate and/or diethyl carbonate.
13. A lithium ion battery, characterized in that it is obtained according to the formation method of any one of claims 1-12.
14. Use of a lithium-ion battery according to claim 13, characterized in that the lithium-ion battery is used in an electric vehicle.
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| CN114204130A (en) | 2022-03-18 |
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