CN111599995A - Cathode material, preparation method thereof and high-voltage lithium ion battery - Google Patents
Cathode material, preparation method thereof and high-voltage lithium ion battery Download PDFInfo
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- CN111599995A CN111599995A CN202010347313.XA CN202010347313A CN111599995A CN 111599995 A CN111599995 A CN 111599995A CN 202010347313 A CN202010347313 A CN 202010347313A CN 111599995 A CN111599995 A CN 111599995A
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- lithium ion
- ion battery
- negative electrode
- voltage lithium
- electrode material
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 239000010406 cathode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000010439 graphite Substances 0.000 claims abstract description 45
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000000853 adhesive Substances 0.000 claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 claims abstract description 30
- 239000007773 negative electrode material Substances 0.000 claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 239000011268 mixed slurry Substances 0.000 claims abstract description 18
- 238000012216 screening Methods 0.000 claims abstract description 18
- 239000011265 semifinished product Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000010426 asphalt Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000011267 electrode slurry Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 239000001768 carboxy methyl cellulose Substances 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007767 bonding agent Substances 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a negative electrode material which comprises graphite particles and an electrolyte-resistant nano metal oxide layer coated on the surfaces of the graphite particles. In addition, the invention also provides a preparation method of the cathode material, which comprises the following steps: 1) dissolving the adhesive in an organic solvent to obtain a diluted adhesive; 2) adding nano metal oxide, diluted adhesive and graphite particles into a metal salt solution to obtain mixed slurry; 3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product; 4) and carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening and demagnetizing to obtain the finished product of the lithium ion battery cathode material. Compared with the prior art, the invention increases the surfaceStructural stability and reduced reactivity, and improved safety.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a negative electrode material, a preparation method of the negative electrode material and a high-voltage lithium ion battery.
Background
Lithium ion batteries gradually come into the sight of people with the characteristics of higher energy density, good cycle performance, no memory effect and the like, and become the focus of attention of researchers in recent years.
The lithium ion battery is a chargeable and dischargeable high-energy battery which mainly comprises an anode, a cathode, a diaphragm, electrolyte and a shell and performs energy exchange by Li + embedding and removing anode and cathode materials. The negative electrode is typically a carbon material, primarily graphite. During the first charge and discharge process of the lithium ion battery, graphite is easy to react with electrolyte on a solid-liquid phase interface to form a passivation film covering the surface of a negative electrode, and the passivation film is called a solid electrolyte interface film, namely an SEI film for short. The degree of crystallinity of the graphite surface is positively correlated with the thermal shock performance, the reaction mechanism is that the graphite with low degree of crystallinity has more surface active sites, and reacts with electrolyte more, SEI decomposes in advance, releases heat, and causes safety (thermal shock) failure.
The existing high voltage rapid charging system is generally coated with carbon on the surface of the negative electrode to improve the rapid charging performance, however, the higher the crystallinity of graphite, the safer the performance is.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the high-voltage lithium ion battery cathode material is provided, the surface structure stability is improved, the reactivity is reduced, and the safety performance is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-voltage lithium ion battery cathode material comprises graphite particles and an electrolyte-resistant nano metal oxide layer coated on the surfaces of the graphite particles.
As an improvement of the high-voltage lithium ion battery cathode material, the mass of the nano metal oxide layer accounts for 10-20% of the mass of the lithium ion battery cathode material.
As an improvement of the high-voltage lithium ion battery cathode material, the thickness of the nano metal oxide layer is 0.01-1 um.
As an improvement of the high-voltage lithium ion battery cathode material, the particle size D50 of the graphite particles is 10-25 um.
The second purpose of the invention is: the preparation method of the high-voltage lithium ion battery cathode material comprises the following steps:
1) dissolving the adhesive in an organic solvent to obtain a diluted adhesive;
2) adding nano metal oxide, diluted adhesive and graphite particles into a metal salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product of the lithium ion battery cathode material;
4) and carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening and demagnetizing to obtain the finished product of the lithium ion battery cathode material.
It should be noted that, the metal ions contained in the metal salt solution are at least partially the same as the metals in the nano metal oxide, and the metal salt solution can not only play a certain role in dispersion, but also a small part of the metals contained in the metal salt solution can be deposited on the surface of the graphite particles to play a certain role in synergy. In addition, since a part of the metal particles may be agglomerated, the part of the impurities is removed by demagnetization in step 4).
As an improvement of the preparation method of the high-voltage lithium ion battery cathode material, the mass ratio of the nano metal oxide to the diluted adhesive to the graphite particles is (60-80) to (10-20).
As an improvement of the preparation method of the high-voltage lithium ion battery cathode material, the particle size of the nano metal oxide is smaller than 1 um. Preferably, the nano metal oxide includes, but is not limited to, at least one of nano aluminum oxide, nano magnesium oxide, nano calcium oxide, nano zinc oxide, nano tin dioxide, nano zirconium dioxide, nano titanium dioxide and nano cerium dioxide.
The adhesive comprises at least one of asphalt, polyacrylate adhesive, organosilicon adhesive, epoxy resin adhesive and polyurethane adhesive; the organic solvent is isopropanol, acetone or ethanol.
The third purpose of the invention is that: the utility model provides a high voltage lithium ion battery, including positive plate, negative pole piece, interval set up in positive plate with diaphragm between the negative pole piece, and electrolyte, the negative pole piece includes the negative pole mass flow body and coat in the negative pole active material on the at least surface of negative pole mass flow body, the negative pole active material be any section in the preceding of description lithium ion battery negative electrode material.
As an improvement of the high-voltage lithium ion battery, the charge cut-off voltage of the battery is more than 4.45V.
Compared with the prior art, the invention at least has the following beneficial effects: according to the invention, the surface of the graphite particle is coated with the electrolysis-resistant nano metal oxide, on one hand, the high-temperature stability of the nano metal oxide is good, and the high-temperature stability of the battery can be improved; on the other hand, the nano metal oxide is uniformly distributed on the surface of the graphite particles, so that the structural stability of the negative electrode material is improved, the reaction activity is reduced, the mutual reaction between the negative electrode material and the electrolyte is reduced, the heat release caused by the early decomposition of SEI is avoided, and the thermal shock performance of the battery is improved.
Drawings
Fig. 1 is an SEM image of nano alumina coated graphite of example 1.
Fig. 2 is an SEM image of the carbon-coated graphite of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
Example 1
Preparing a positive plate: uniformly mixing lithium cobaltate (the charge cut-off voltage is more than 4.45V), conductive carbon and an adhesive (polyvinylidene fluoride) in an N-methyl pyrrolidone solvent according to the mass ratio of 97:1.5:1.5 to prepare anode slurry, then coating the anode slurry on an aluminum foil, drying the aluminum foil, and performing cold pressing and strip division to prepare the anode sheet.
Preparing a negative plate:
1) dissolving asphalt in acetone to obtain diluted asphalt;
2) adding nano alumina, diluted asphalt and graphite particles (the particle size is 15um) into an aluminum salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product;
4) carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening and demagnetizing to obtain graphite coated with the nano aluminum oxide layer;
5) uniformly mixing graphite coated with the nano aluminum oxide layer, conductive carbon, a dispersing agent (sodium carboxymethylcellulose) and a bonding agent (styrene butadiene rubber) in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare negative electrode slurry, then coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and strip division to prepare the negative electrode sheet.
Preparing a battery: winding the positive plate, the conventional diaphragm and the negative plate into a battery cell, leading out the positive electrode by spot welding of an aluminum tab, and leading out the negative electrode by spot welding of a nickel tab; then the cell is placed in an aluminum-plastic packaging bag, high-voltage electrolyte is injected, and the cell is prepared through the procedures of packaging, formation and capacity grading.
Example 2
Different from example 1, the preparation of the negative electrode sheet:
1) dissolving asphalt in isopropanol to obtain diluted asphalt;
2) adding nano magnesium oxide, diluted asphalt and graphite particles (the particle size is 20um) into the magnesium salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product;
4) carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening and demagnetizing to obtain graphite coated with a nano magnesium oxide layer;
5) uniformly mixing graphite coated with the nano magnesium oxide layer, conductive carbon, a dispersing agent (sodium carboxymethylcellulose) and a bonding agent (styrene butadiene rubber) in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare negative electrode slurry, then coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and strip division to prepare the negative electrode sheet.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
Different from example 1, the preparation of the negative electrode sheet:
1) dissolving a polyacrylate adhesive in acetone to obtain a diluted polyacrylate adhesive;
2) adding nano calcium oxide, diluted polyacrylate adhesive and graphite particles (the particle size is 10um) into the calcium salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product;
4) carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening, and demagnetizing to obtain graphite coated with a nano calcium oxide layer;
5) uniformly mixing graphite coated with the nano calcium oxide layer, conductive carbon, a dispersing agent (sodium carboxymethylcellulose) and a bonding agent (styrene butadiene rubber) in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare negative electrode slurry, then coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and strip division to prepare the negative electrode sheet.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
Different from example 1, the preparation of the negative electrode sheet:
1) dissolving an organic silicon adhesive in acetone to obtain a diluted organic silicon adhesive;
2) adding nano zinc oxide, diluted organic silicon adhesives and graphite particles (the particle size is 12um) into a zinc salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product;
4) carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening and demagnetizing to obtain graphite coated with nano zinc oxide;
5) uniformly mixing graphite coated with a nano zinc oxide layer, conductive carbon, a dispersing agent (sodium carboxymethylcellulose) and a bonding agent (styrene butadiene rubber) in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare negative electrode slurry, then coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and strip division to prepare the negative electrode sheet.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
Different from example 1, the preparation of the negative electrode sheet:
1) dissolving an epoxy resin adhesive in acetone to obtain a diluted epoxy resin adhesive;
2) adding nano magnesium oxide, nano aluminum oxide, diluted epoxy resin adhesive and graphite particles (the particle size is 18um) into an aluminum salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product;
4) carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening, and demagnetizing to obtain graphite coated with nano aluminum oxide and nano magnesium oxide;
5) uniformly mixing graphite coated with nano metal aluminum oxide and magnesium oxide, conductive carbon, a dispersant (sodium carboxymethyl cellulose) and an adhesive (styrene butadiene rubber) in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare negative electrode slurry, then coating the negative electrode slurry on a copper foil, drying, and carrying out cold pressing and strip division to prepare a negative electrode sheet.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
Different from example 1, the preparation of the negative electrode sheet:
1) dissolving a polyurethane adhesive in acetone to obtain a diluted polyurethane adhesive;
2) adding nano magnesium oxide, nano aluminum oxide, diluted polyurethane adhesive and graphite particles (the particle size is 25um) into the magnesium salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product;
4) carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening, and demagnetizing to obtain graphite coated with nano aluminum oxide and nano magnesium oxide;
5) uniformly mixing graphite coated with nano metal aluminum oxide and magnesium oxide, conductive carbon, a dispersant (sodium carboxymethyl cellulose) and an adhesive (styrene butadiene rubber) in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare negative electrode slurry, then coating the negative electrode slurry on a copper foil, drying, and carrying out cold pressing and strip division to prepare a negative electrode sheet.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
Different from example 1, the preparation of the negative electrode sheet:
uniformly mixing graphite coated with carbon, a conductive carbon dispersant (sodium carboxymethylcellulose) and a binder (styrene butadiene rubber) in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare negative electrode slurry, then coating the negative electrode slurry on a copper foil, drying, cold pressing and slitting to prepare a negative electrode sheet.
The rest is the same as embodiment 1, and the description is omitted here.
Performance testing
1) The nano alumina layer-coated graphite obtained in example 1 and the carbon-coated graphite obtained in the comparative example were respectively subjected to electron scanning, and SEM images obtained were respectively shown in fig. 1 to 2.
2) TG-MS test: the exothermic peak temperatures of the negative electrode materials prepared in examples 1 to 6 and comparative example 1 were measured to determine the thermal stability of the negative electrode materials, and the test results are shown in table 1.
3) And (3) testing thermal shock performance: 5 of the batteries prepared in examples 1 to 6 and comparative example 1 were placed in an environment with an initial temperature of 20 + -5 deg.C, heated to 135 + -2 deg.C at a rate of 5 + -2 deg.C and kept for 10 minutes, and the number of the batteries passing the thermal shock performance test was recorded, and "no smoke, no fire, no explosion" was "passed". The test results are shown in Table 1.
TABLE 1 test results
As can be seen from comparison between fig. 1 and fig. 2, the negative electrode material prepared in the present invention has metal alumina particles (white bright spots) uniformly distributed on the graphite surface, and has fewer active sites; the negative electrode material prepared in comparative example 1 had more active sites.
In addition, as can be seen from the test data in table 1, the exothermic peak temperature of the negative electrode material prepared by the present invention is significantly higher than that of the comparative example 1, and it can be seen that the thermal stability is high, and when the thermal shock performance test is performed, the passing rate of the battery prepared by using the negative electrode material of the present invention is still 100% at 137 ℃, whereas the passing rate of the battery prepared by using the negative electrode material of the comparative example 1 is reduced to about 20% at 132 ℃ and reduced to 0 at 135 ℃. Therefore, the anode material disclosed by the invention is beneficial to improving the thermal shock performance of the battery. The cathode material has few active sites, so that the mutual reaction between the cathode material and an electrolyte is reduced, and the heat release caused by the premature decomposition of SEI is avoided, thereby improving the safety performance of the battery.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The negative electrode material of the high-voltage lithium ion battery is characterized by comprising graphite particles and an electrolyte-resistant nano metal oxide layer coated on the surfaces of the graphite particles.
2. The high voltage lithium ion battery negative electrode material of claim 1, wherein: the mass of the nano metal oxide layer accounts for 10-20% of the lithium ion battery cathode material.
3. The negative electrode material of the high-voltage lithium ion battery as claimed in claim 1, wherein the thickness of the nano metal oxide layer is 0.01-1 um.
4. The negative electrode material for the high-voltage lithium ion battery of claim 1, wherein the graphite particles have a particle size D50 of 10-25 um.
5. A preparation method of a high-voltage lithium ion battery cathode material is characterized by comprising the following steps:
1) dissolving the adhesive in an organic solvent to obtain a diluted adhesive;
2) adding nano metal oxide, diluted adhesive and graphite particles into a metal salt solution to obtain mixed slurry;
3) adjusting the pH of the mixed slurry<10, introduction of CO2Stirring and reacting for 1-5 h, performing suction filtration, washing, drying, grinding and screening to obtain a semi-finished product of the lithium ion battery cathode material;
4) and carbonizing the obtained semi-finished product at 500-1000 ℃, crushing, screening and demagnetizing to obtain the finished product of the lithium ion battery cathode material.
6. The method for preparing the negative electrode material of the high-voltage lithium ion battery as claimed in claim 5, wherein the mass ratio of the nano metal oxide to the diluted binder to the graphite particles is (60-80): (10-20): (10-20).
7. The method for preparing the negative electrode material of the high-voltage lithium ion battery according to claim 5, wherein the nano metal oxide has a particle size of less than 1 um.
8. The method for preparing the negative electrode material of the high-voltage lithium ion battery according to claim 5, wherein the binder comprises at least one of asphalt, polyacrylate binder, silicone binder, epoxy resin binder, and polyurethane binder; the organic solvent is isopropanol, acetone or ethanol.
9. A high-voltage lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate at intervals, and electrolyte, wherein the negative plate comprises a negative current collector and a negative active substance coated on at least one surface of the negative current collector, and the negative active substance is the lithium ion battery negative electrode material in any one of claims 1-8.
10. The high voltage lithium ion battery of claim 9, wherein: the charge cutoff voltage of the battery is greater than 4.45V.
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