CN118048675A - High-nickel monocrystal positive electrode material for lithium ion battery, preparation method and low-temperature electrolyte - Google Patents
High-nickel monocrystal positive electrode material for lithium ion battery, preparation method and low-temperature electrolyte Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 239000003792 electrolyte Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 57
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 11
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- NONFLFDSOSZQHR-UHFFFAOYSA-N 3-(trimethylsilyl)propionic acid Chemical compound C[Si](C)(C)CCC(O)=O NONFLFDSOSZQHR-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 39
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 26
- -1 FEC Chemical compound 0.000 description 20
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 15
- 239000010406 cathode material Substances 0.000 description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 15
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 15
- MZMVVHAHSRJOEO-UHFFFAOYSA-N 1-chloropropylbenzene Chemical compound CCC(Cl)C1=CC=CC=C1 MZMVVHAHSRJOEO-UHFFFAOYSA-N 0.000 description 9
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 9
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- OIIWPAYIXDCDNL-UHFFFAOYSA-M sodium 3-(trimethylsilyl)propionate Chemical compound [Na+].C[Si](C)(C)CCC([O-])=O OIIWPAYIXDCDNL-UHFFFAOYSA-M 0.000 description 6
- VUZHZBFVQSUQDP-UHFFFAOYSA-N 4,4,5,5-tetrafluoro-1,3-dioxolan-2-one Chemical compound FC1(F)OC(=O)OC1(F)F VUZHZBFVQSUQDP-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- SUYRLXYYZQTJHF-VMBLUXKRSA-N dalfopristin Chemical compound O=C([C@@H]1N(C2=O)CC[C@H]1S(=O)(=O)CCN(CC)CC)O[C@H](C(C)C)[C@H](C)\C=C\C(=O)NC\C=C\C(\C)=C\[C@@H](O)CC(=O)CC1=NC2=CO1 SUYRLXYYZQTJHF-VMBLUXKRSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-nickel monocrystal positive electrode material for a lithium ion battery, a preparation method and a low-temperature electrolyte, which comprise five steps of preparing a LiNi aCobMncO2 polycrystal ternary positive electrode material, putting the material into a sintering furnace for sintering, cooling after sintering, crushing by adopting a ball milling crushing technology, finally sintering, and taking out the monocrystal LiNi aCobMncO2 positive electrode material after sintering.
Description
Technical Field
The invention relates to the technical field of cathode materials and electrolyte in lithium batteries, in particular to a high-nickel monocrystal cathode material for lithium ion batteries, a preparation method and low-temperature electrolyte.
Background
The lithium battery is a battery using a nonaqueous electrolyte solution and using lithium metal or lithium alloy as a positive/negative electrode material, and the lithium metal has very high requirements on environment due to the very active chemical characteristics of the lithium metal. With the development of science and technology, lithium batteries have become the mainstream, and lithium batteries can be broadly divided into two types: lithium metal batteries and lithium ion batteries. The lithium ion battery does not contain metallic lithium, can be charged, and has better safety, specific capacity, self-discharge rate and cost performance than the lithium ion battery.
While positive electrode materials of high nickel layered polycrystalline morphology have been commercialized and tend to mature. As the polycrystalline material particles are secondary particles agglomerated by primary particles, anisotropic stress exists in the circulating process, micro cracks can be generated by the secondary particles along with the promotion of the circulating process, and electrolyte is permeated, the high-nickel polycrystalline positive electrode material is required to be manufactured into a high-nickel single crystal positive electrode material, and the micro cracks are not easy to generate due to no grain boundary in the single crystal, so that the occurrence of interface side reaction can be effectively inhibited, the high-nickel single crystal positive electrode material has better circulating performance and thermal stability, but in the prior art, the process for preparing the high-nickel single crystal positive electrode material is more complex, and the whole preparation time cost and energy consumption cost are improved.
Further, for the lithium ion battery, the lithium ion battery also comprises electrolyte, wherein the electrolyte is a medium (with certain corrosiveness) used by a chemical battery, an electrolytic capacitor and the like, ions are provided for normal operation of the electrolyte, and chemical reactions occurring in the operation are guaranteed to be reversible, but in the prior art, the performance of the electrolyte is correspondingly influenced under the low-temperature environment to cause the performance of the lithium ion battery to be reduced, so the high-nickel single crystal positive electrode material for the lithium battery, the preparation method and the low-temperature electrolyte are provided to solve the problems in the prior art.
Disclosure of Invention
The invention aims to provide the high-nickel single crystal positive electrode material for the lithium ion battery, the preparation method and the low-temperature electrolyte, and the high-nickel single crystal positive electrode material for the lithium ion battery, the preparation method and the low-temperature electrolyte have the advantages of simple process and low energy consumption, and can adapt to the low-temperature environment, so that the problems in the prior art can be solved.
In order to achieve the purpose of the invention, the invention is realized by the following technical scheme: the preparation method of the high-nickel monocrystal positive electrode material for the lithium ion battery comprises the following steps:
Step one: preparing a LiNi aCobMncO2 polycrystal ternary positive electrode material;
Step two: placing the LiNi aCobMncO2 polycrystal ternary anode material into a sintering furnace, and sintering after the sintering temperature is increased to 750-950 ℃;
Step three: taking out and cooling after sintering, cooling to normal temperature, and putting into a ball mill for ball milling and crushing to obtain crushed materials;
Step four: putting the obtained crushed material into a sintering furnace again, and sintering after the sintering temperature is increased to 700-850 ℃;
step five: and taking out and cooling after sintering to obtain the monocrystal LiNi aCobMncO2 anode material.
The further improvement is that: in the second step, the sintering time is 10-18h.
The further improvement is that: in the third step, the rotating speed of the ball mill is 250-350rpm/min, and the ball milling time is 1-6h.
The further improvement is that: in the fourth step, the sintering time is consistent with the sintering time in the second step.
The high-nickel single crystal positive electrode material for the lithium ion battery is prepared by the method of claims 1-4.
The low-temperature electrolyte for the lithium ion battery comprises the following raw materials in molar mass ratio: 8-20% of lithium salt, 75-85% of organic solvent and 1-7% of film forming additive.
The further improvement is that: the lithium salt is any four substance combinations in LiPF 6、LiDFOB、LiBF4、LiPO2F2、LiTFSi、LiFSI、KNO3.
The further improvement is that: the organic solvent is any three substance combinations in EC, EMC, DMC, DOL, DME.
The further improvement is that: the film forming additive is any three substance combinations in VC, FEC, TMSP, EBC, EC.
The beneficial effects of the invention are as follows: the high-nickel monocrystal positive electrode material for the lithium battery, the preparation method and the low-temperature electrolyte are characterized in that the polycrystalline ternary positive electrode material is calcined, ball milling and crushing are carried out in a ball milling crushing mode, then the calcination is carried out, the high-nickel monocrystal positive electrode material is prepared through controlling the temperature and the calcination time, the high-nickel monocrystal positive electrode material is suitable for high-nickel ternary positive electrode material products with different performance requirements, the high-temperature calcination and ball milling combined strategy is adopted, the process is simple, the energy consumption is low, the large-scale preparation of the high-performance lithium ion battery positive electrode material can be realized, the morphology of the obtained monocrystal positive electrode material is better, and the electrochemical performance of the lithium ion battery working at low temperature is further improved by adjusting the composition and the consumption of lithium salt, solvent and film forming additive of the electrolyte.
Drawings
FIG. 1 is a schematic view showing a process for producing a high nickel single crystal positive electrode material of the present invention.
FIG. 2 is a schematic diagram of the morphology of a high nickel positive electrode material prepared according to the second embodiment of the present invention.
FIG. 3 is a schematic drawing showing the HRTEM of the high nickel single crystal positive electrode material and the Fourier transform of the selected region according to the second embodiment of the present invention.
Fig. 4 is a graph showing the cycle retention rate at low temperature of a lithium ion battery assembled from the high nickel single crystal positive electrode material and the low temperature electrolyte solution of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following examples, which are only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
In the following examples, 0.6.ltoreq.a < 1, 0.01.ltoreq.b.ltoreq.0.2, 0.01.ltoreq.c.ltoreq.0.2, and a+b+c=1 in the LiNi aCobMncO2 polycrystalline ternary cathode material, 0.6.ltoreq.a < 1, 0.01.ltoreq.b.ltoreq.0.2, 0.01.ltoreq.c.ltoreq.0.2, and a+b+c=1 in the single crystal LiNi aCobMncO2 cathode material.
Examples
According to the embodiment shown in fig. 1, a preparation method of a high nickel single crystal positive electrode material for a lithium ion battery is provided, which comprises the following steps:
Step one: preparing a LiNi 0.6Co0.2Mn0.2O2 polycrystal ternary positive electrode material;
step two: placing the LiNi 0.6Co0.2Mn0.2O2 polycrystal ternary anode material into a sintering furnace, and sintering for 10 hours after the sintering temperature is increased to 750 ℃;
Step three: taking out and cooling after sintering, cooling to normal temperature, and putting into a ball mill for ball milling and crushing to obtain crushed materials, wherein the rotation speed of the ball mill is 350rpm/min, and the ball milling time is 1h;
step four: putting the obtained crushed material into a sintering furnace again, and after the sintering temperature is increased to 700 ℃, sintering for 10 hours, wherein the sintering time is consistent with the sintering time in the second step;
Step five: and taking out and cooling after sintering to obtain the monocrystal LiNi 0.6Co0.2Mn0.2O2 anode material.
The high-nickel single crystal positive electrode material for the lithium ion battery is prepared by adopting the method.
The low-temperature electrolyte for the lithium ion battery comprises the following raw materials in molar mass ratio: 8% of lithium salt, 85% of organic solvent and 7% of film forming additive.
Wherein the lithium salt is any four combination of materials of LiPF 6 (lithium hexafluorophosphate), liPF ob (lithium difluorooxalato borate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate), liTFSi (lithium bistrifluoro-methanesulfonimide), liFSI (lithium bisfluoro-sulfonyl imide salt), KNO 3 (potassium nitrate), in this example the lithium salt is LiPF 6 (lithium hexafluorophosphate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate) and LiSFI (lithium bisfluoro-sulfonyl imide salt) composition, wherein the ratio between LiPF 6 (lithium hexafluorophosphate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate) and LiSFI (lithium bisfluoro-sulfonyl imide salt) is: 85:3:1:3.
The organic solvent is any three material combinations of EC (ethylene carbonate), EMC (methyl ethyl carbonate), DMC (dimethyl carbonate), DOL (1, 3-dioxolane) and DME (dimethyl ether), and in the embodiment, the organic solvent is a combination of EC (ethylene carbonate), EMC (methyl ethyl carbonate) and DMC (dimethyl carbonate), wherein the ratio of the organic solvents EC (ethylene carbonate), EMC (methyl ethyl carbonate) and DMC (dimethyl carbonate) is 1:1:1.
The film forming additive is any three of VC (vinylene carbonate), FEC (perfluoroethylene carbonate), TMSP (tris (trimethylsilane) phosphate), EBC (ethylbenzyl chloride) and EC (ethylene carbonate), and in this example, the film forming additive is a combination of VC (vinylene carbonate), FEC (perfluoroethylene carbonate) and EBC (ethylbenzyl chloride) with a ratio of 3:15:6 between VC (vinylene carbonate), FEC (perfluoroethylene carbonate) and EBC (ethylbenzyl chloride).
Examples
According to the fig. 1-4, this embodiment provides a method for preparing a high nickel single crystal positive electrode material for a lithium ion battery, comprising the following steps:
Step one: preparing a LiNi 0.8Co0.1Mn0.1O2 polycrystal ternary positive electrode material;
step two: placing the LiNi 0.8Co0.1Mn0.1O2 polycrystal ternary anode material into a sintering furnace, and sintering for 13 hours after the sintering temperature is increased to 950 ℃;
Step three: taking out and cooling after sintering, cooling to normal temperature, and putting into a ball mill for ball milling and crushing to obtain crushed materials, wherein the rotating speed of the ball mill is 250rpm/min, and the ball milling time is 6 hours;
step four: putting the obtained crushed material into a sintering furnace again, and after the sintering temperature is increased to 850 ℃, sintering, wherein the sintering time is consistent with the sintering time in the second step, namely 13h;
Step five: and taking out and cooling after sintering to obtain the monocrystal LiNi 0.8Co0.1Mn0.1O2 anode material.
The high-nickel single crystal positive electrode material for the lithium ion battery is prepared by adopting the method.
The low-temperature electrolyte for the lithium ion battery comprises the following raw materials in molar mass ratio: 20% of lithium salt, 75% of organic solvent and 5% of film forming additive,
Wherein the lithium salt is any four combination of LiPF 6 (lithium hexafluorophosphate), liPF ob (lithium difluorooxalato borate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate), liTFSi (lithium bistrifluoro-methanesulfonimide), liSFI (lithium bisfluoro-sulfonyl imide salt), KNO 3 (potassium nitrate), in this example the lithium salt is LiPF 6 (lithium hexafluorophosphate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate) and LiSFI (lithium bisfluoro-sulfonyl imide salt) composition, wherein the ratio between LiPF 6 (lithium hexafluorophosphate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate) and LiSFI (lithium bisfluoro-sulfonyl imide salt) is: 85:3:1:3.
The organic solvent is any three substances selected from EC (ethylene carbonate), EMC (methyl ethyl carbonate), DMC (dimethyl carbonate), DOL (1, 3-dioxolane) and DME (dimethyl ether), and in the embodiment, the organic solvent is a composition of DMC (dimethyl carbonate), DOL (1, 3-dioxolane) and DME (dimethyl ether), wherein the ratio of DMC (dimethyl carbonate), DOL (1, 3-dioxolane) and DME (dimethyl ether) is 1:1:1.
The film forming additive is any three of VC (vinylene carbonate), FEC (perfluoroethylene carbonate), TMSP (tris (trimethylsilane) phosphate), EBC (ethylbenzyl chloride) and EC (ethylene carbonate), and in the embodiment, the film forming additive is a composition of TMSP (tris (trimethylsilane) phosphate), EBC (ethylbenzyl chloride) and EC (ethylene carbonate), and the ratio of TMSP (tris (trimethylsilane) phosphate), EBC (ethylbenzyl chloride) and EC (ethylene carbonate) is 1:25:2.
As shown in fig. 2, which is a scanning electron microscope image of the sample prepared in this example, the sample in this example has a uniform single crystal structure, almost no secondary particles are aggregated, and as shown in fig. 3, the sample in this example has a mainly layered structure, and the phase is consistent with LiNiO 2, which indicates that the high nickel single crystal positive electrode material was successfully prepared.
Examples
According to the fig. 1-4, this embodiment provides a method for preparing a high nickel single crystal positive electrode material for a lithium ion battery, comprising the following steps:
step one: preparing a LiNi 0.9Co0.05Mn0.05O2 polycrystal ternary positive electrode material;
Step two: placing the LiNi 0.9Co0.05Mn0.05O2 polycrystal ternary anode material into a sintering furnace, and sintering for 18 hours after the sintering temperature is increased to 880 ℃;
Step three: taking out and cooling after sintering, cooling to normal temperature, and putting into a ball mill for ball milling and crushing to obtain crushed materials, wherein the rotating speed of the ball mill is 300rpm/min, and the ball milling time is 3 hours;
step four: putting the obtained crushed material into a sintering furnace again, and after the sintering temperature is increased to 800 ℃, sintering, wherein the sintering time is consistent with the sintering time in the second step, namely 18 hours;
Step five: and taking out and cooling after sintering to obtain the monocrystal LiNi 0.9Co0.05Mn0.05O2 anode material.
The high-nickel single crystal positive electrode material for the lithium ion battery is prepared by adopting the method.
The low-temperature electrolyte for the lithium ion battery comprises the following raw materials in molar mass ratio: 19% of lithium salt, 80% of organic solvent and 1% of film forming additive.
Wherein the lithium salt is any four combination of materials from LiPF 6 (lithium hexafluorophosphate), liPF ob (lithium difluorooxalato borate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate), liTFSi (lithium bistrifluoromethane sulfonyl imide), in this example the lithium salt is a combination of LiPF 6 (lithium hexafluorophosphate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate) and LiSFI, wherein the ratio (molar ratio) between LiPF 6 (lithium hexafluorophosphate), liBF 4 (lithium tetrafluoroborate), liPO 2F2 (lithium difluorophosphate) and LiSFI is: 85:3:1:3.
The organic solvent is any three substances selected from EC (ethylene carbonate), EMC (methyl ethyl carbonate), DMC (dimethyl carbonate), DOL (1, 3-dioxolane) and DME (dimethyl ether), and in the embodiment, the organic solvent is a composition of EMC (methyl ethyl carbonate), DME (dimethyl ether) and DOL (1, 3-dioxolane), wherein the ratio of the EMC (methyl ethyl carbonate), DOL (1, 3-dioxolane) and DME (dimethyl ether) is 1:1:1.
The film forming additive is any three of VC (vinylene carbonate), FEC (perfluoroethylene carbonate), TMSP (tris (trimethylsilane) phosphate), EBC (ethylbenzyl chloride) and EC (ethylene carbonate), and in the embodiment, the film forming additive is a combination of VC (vinylene carbonate), EBC (ethylbenzyl chloride) and EC (ethylene carbonate). The ratio between VC (vinylene carbonate), EBC (ethylbenzyl chloride) and EC (ethylene carbonate) is: 1:25:2.
According to the method, the high-nickel monocrystal ternary cathode material prepared by the method is used as a cathode, metal lithium is used as an anode, a lithium ion battery is formed by the metal lithium and low-temperature electrolyte, and then the long cycle performance of the lithium ion battery at the temperature of minus 20 ℃ is tested, as shown in figure 4, after the high-nickel monocrystal ternary cathode material prepared by the method II and the method III are cycled for 100 times at the temperature of minus 20 ℃ and the current density of 1C, the capacity retention rate is higher than that of the high-nickel monocrystal cathode material prepared by the method I and the method III, wherein the capacity retention rate is obviously improved in the second embodiment compared with that of the high-nickel monocrystal cathode material prepared by the method I and the method III after 100 times of cycling, and the cycle performance stability of the lithium ion battery at the low temperature can be obviously improved by combining the low-temperature electrolyte.
The invention adopts the method of calcining the polycrystalline ternary cathode material, ball-milling and crushing the polycrystalline ternary cathode material, then calcining the polycrystalline ternary cathode material, preparing the high-nickel monocrystal cathode material integrally by controlling the temperature and the calcining time, being applicable to high-nickel ternary cathode material products with different performance requirements, adopting a strategy of high-temperature calcining combined with ball milling, having simple process and low energy consumption, being capable of realizing large-scale preparation of high-performance lithium ion battery cathode materials, having better appearance of the obtained monocrystal cathode material, further improving the electrochemical performance of the lithium ion battery working at low temperature by adjusting the composition and the dosage of lithium salt, solvent and film forming additive of the electrolyte, adapting to low-temperature environment and ensuring the working efficiency of the lithium ion battery.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents.
Claims (9)
1. The preparation method of the high-nickel monocrystal positive electrode material for the n1. lithium ion battery is characterized by comprising the following steps of: the method comprises the following steps:
Step one: preparing a LiNi aCobMncO2 polycrystal ternary positive electrode material;
Step two: placing the LiNi aCobMncO2 polycrystal ternary anode material into a sintering furnace, and sintering after the sintering temperature is increased to 750-950 ℃;
Step three: taking out and cooling after sintering, cooling to normal temperature, and putting into a ball mill for ball milling and crushing to obtain crushed materials;
Step four: putting the obtained crushed material into a sintering furnace again, and sintering after the sintering temperature is increased to 700-850 ℃;
step five: and taking out and cooling after sintering to obtain the monocrystal LiNi aCobMncO2 anode material.
2. The method for producing a high nickel single crystal positive electrode material for lithium ion batteries according to claim 1, characterized in that: in the second step, the sintering time is 10-18h.
3. The method for producing a high nickel single crystal positive electrode material for lithium ion batteries according to claim 1, characterized in that: in the third step, the rotating speed of the ball mill is 250-350rpm/min, and the ball milling time is 1-6h.
4. The method for producing a high nickel single crystal positive electrode material for lithium ion batteries according to claim 1, characterized in that: in the fourth step, the sintering time is consistent with the sintering time in the second step.
5. The high nickel monocrystal positive electrode material for the lithium ion battery is characterized in that: the high-nickel monocrystal positive electrode material for the lithium battery is prepared by adopting the method of claims 1-4.
6. The low-temperature electrolyte for the lithium ion battery is characterized in that: the low-temperature electrolyte for the lithium battery comprises the following raw materials in molar mass ratio: 8-20% of lithium salt, 75-85% of organic solvent and 1-7% of film forming additive.
7. The method for producing a high nickel single crystal positive electrode material for lithium ion batteries according to claim 6, characterized in that: the lithium salt is any four substance combinations in LiPF 6、LiDFOB、LiBF4、LiPO2F2、LiTFSi、LiFSI、KNO3.
8. The method for producing a high nickel single crystal positive electrode material for lithium ion batteries according to claim 6, characterized in that: the organic solvent is any three substance combinations in EC, EMC, DMC, DOL, DME.
9. The method for producing a high nickel single crystal positive electrode material for lithium ion batteries according to claim 6, characterized in that: the film forming additive is any three substance combinations in VC, FEC, TMSP, EBC, EC.
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