CN112397719A - Hydrophobic lithium battery positive electrode material, positive electrode and preparation method thereof - Google Patents
Hydrophobic lithium battery positive electrode material, positive electrode and preparation method thereof Download PDFInfo
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- 239000007774 positive electrode material Substances 0.000 title claims description 33
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 230000008595 infiltration Effects 0.000 abstract description 3
- 238000001764 infiltration Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004886 process control Methods 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000265 homogenisation Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010294 electrolyte impregnation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 preferably Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement 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
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A hydrophobic lithium battery anode material, an anode and a preparation method thereof are provided, the hydrophobic lithium battery anode material is a conventional lithium battery anode material surface combined with a hydrophobic modifier, wherein the molecular structure of the hydrophobic modifier is R-Xn(ii) a R is alkyl with 6-18 carbon atoms optionally having substituent selected from alkyl, aryl or alkoxy; x is-Si- (R)2)3OR1Or a carboxyl group, R1、R2Is methyl or ethyl; n is 1, 2, 3 or 4. The cathode material is not easy to absorb moisture in the electrode preparation and electrode circulation processes, reduces the difficulty of electrode process control, and is beneficial to the improvement of the moisture control of a pole piece and the infiltration characteristic of electrolyte.
Description
Technical Field
The invention relates to a hydrophobic lithium battery positive electrode material, a positive electrode and a preparation method thereof, and belongs to the technical field of lithium battery electrode materials.
Background
The lithium battery is very sensitive to moisture, and high moisture can cause SEI film decomposition, electrolyte decomposition and side reaction aggravation, so that battery efficiency is reduced, capacity is attenuated, gas generation is expanded, and even fire and explosion accidents are generated in serious cases. Therefore, the electrode is assembled into a battery, and the moisture of the electrode is controlled within a required range before liquid injection. In order to ensure that the electrode moisture meets the control requirement, the humidity of the production environment of the working procedures of battery preparation, assembly, liquid injection and the like is usually-35 to-40 ℃ dew point temperature, and meanwhile, the electrode and the battery core need to be strictly vacuum-baked to meet the moisture control requirement.
Most of the positive electrode materials are metal oxides, have certain hydrophilicity, and are easy to form crystal water with moisture in the air or to generate physical adsorption. Particularly, the high nickel anode material has reduced stability due to the increase of nickel content, and the surface alkali content is increased, so that the high nickel anode material is easy to absorb moisture and carbon dioxide in the air, which causes a lot of troubles to the manufacturing process of the battery. For example, gelation easily occurs during the homogenization stage, which results in unusable slurry or poor slurry stability; in the electrode circulation process, the consistency of the battery performance is difficult to control due to the difference between the process control and the circulation time. The proportion of the positive electrode material in the positive electrode plate is more than 90%, and the positive electrode material is a main source of electrode moisture, so that the moisture control of the positive electrode material becomes the key of the whole positive electrode moisture control.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a positive electrode material, wherein a silyl ether or carboxyl functional group (-X) of a modifier is covalently linked to a hydroxyl group (-M-OH) or an oxygen terminal group (-M ═ O) on the surface of the positive electrode material, and a hydrophobic chain (R-) of the modifier is linked to the surface of the positive electrode material, so as to form a hydrophobic protective layer on the surface of the positive electrode material, thereby reducing the moisture content and water absorption capacity of the positive electrode material. Meanwhile, after hydrophobic modification, the electrolyte infiltration characteristic of the positive pole piece can be improved.
In order to achieve the purpose, the invention provides the following technical scheme:
the hydrophobic lithium battery anode material is prepared by combining a hydrophobic modifier on the surface of a conventional lithium battery anode material, wherein the molecular structure of the hydrophobic modifier is R-Xn(ii) a R is alkyl with 6-18 carbon atoms optionally having substituent selected from alkyl, aryl or alkoxy; x is-Si- (R)2)3OR1Or a carboxyl group, R1、R2Is methyl or ethyl; n is 1, 2, 3 or 4.
As described above, the hydrophobic lithium battery cathode material is preferably lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium cobalt oxide or lithium nickel oxide.
In the hydrophobic lithium battery cathode material, the nickel cobalt lithium manganate is preferably 111 type, 424 type, 523 type, 622 type, 711 type or 811 type.
The hydrophobic lithium battery cathode material is characterized in that the mass ratio of the conventional lithium battery cathode material to the hydrophobic modifier is 1: 0.0001 to 0.1.
In another aspect, the present invention provides a method for preparing the hydrophobic lithium battery positive electrode material, the method comprising: dispersing the conventional lithium battery positive electrode material in a polar solvent, adding the hydrophobic modifier, uniformly mixing, filtering and drying to obtain the hydrophobic lithium battery positive electrode material.
In the preparation method of the hydrophobic lithium battery cathode material, preferably, the polar solvent is NMP or ethanol.
In another aspect, the invention provides a hydrophobic lithium battery positive electrode, which adopts the hydrophobic lithium battery positive electrode material.
In another aspect, the present invention provides a method for preparing a hydrophobic lithium battery positive electrode as described above, the method comprising: homogenizing the hydrophobic lithium battery positive electrode material, and then coating the slurry on a positive electrode substrate to prepare the hydrophobic lithium battery positive electrode.
In another aspect, the present invention provides a method for preparing a hydrophobic lithium battery positive electrode as described above, the method comprising: homogenizing the positive electrode material of the conventional lithium battery, adding the hydrophobic modifier into the slurry, uniformly mixing to prepare hydrophobic positive electrode slurry, and then coating the slurry on a positive electrode substrate to prepare the hydrophobic lithium battery positive electrode.
The invention has the beneficial effects that: the surface of the hydrophobic lithium battery positive electrode material is provided with the hydrophobic modification layer, so that moisture is not easily absorbed in the electrode preparation and electrode circulation processes, the moisture control difficulty in the electrode preparation process is reduced, the improvement of the pole piece moisture control and the electrolyte infiltration characteristic is facilitated, and the first-round efficiency and the circulation capacity of the electrode are improved.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
1. Preparation of hydrophobic lithium battery cathode material
100g of 811 type lithium nickel cobalt manganese oxide was dispersed in 500mL of ethanol, and 0.05g (CH) was added3)3-Si-OCH2CH3And uniformly mixing, filtering and drying to obtain the hydrophobic lithium battery cathode material.
2. Positive pole piece of hydrophobic lithium battery
2.1 homogenization: adding 40g of carbon tube slurry (5% of solid content), 20g of conductive carbon black and 500g of PVDF (polyvinylidene fluoride) glue solution (6%) into 2000g of the hydrophobic lithium battery anode material prepared in the step 1, stirring for half an hour by using a homogenizer at 15rpm, adding 500g of PVDF glue solution (6%) and 200mLNMP, and filtering the slurry by using a 200-mesh filter screen;
2.2 coating androlling: coating the slurry on a 13-micron thick aluminum foil with an areal density of 15mg/cm2(ii) a And rolling the pole piece, wherein the thickness of the positive pole material is 45 mu m, and preparing the hydrophobic lithium battery positive pole.
2.3 the pole piece is subjected to the processes of sheet making, assembling and formation to prepare the full battery for performance test, the first effect is 86.6 percent, and the cycle life is 95.3 percent in 500 weeks.
Example 2
1. Preparation of hydrophobic lithium battery cathode material
Dispersing 100g 622 type nickel cobalt lithium manganate in 500mL ethanol, adding 0.03g CH3(CH2)15-Si-OCH2CH3And uniformly mixing, filtering and drying to obtain the hydrophobic lithium battery cathode material.
2. Positive pole piece of hydrophobic lithium battery
2.1 homogenization: adding 40g of carbon tube slurry (5% of solid content), 20g of conductive carbon black and 500g of PVDF (polyvinylidene fluoride) glue solution (6%) into 2000g of the hydrophobic lithium battery anode material prepared in the step 1, stirring for half an hour by using a homogenizer at 15rpm, adding 500g of PVDF glue solution (6%) and 200mLNMP, and filtering the slurry by using a 200-mesh filter screen;
2.2 coating and rolling: coating the slurry on a 13-micron thick aluminum foil with an areal density of 15mg/cm2(ii) a And rolling the pole piece, wherein the thickness of the positive pole material is 45 mu m, and preparing the hydrophobic lithium battery positive pole.
2.3 the pole piece is subjected to the processes of sheet making, assembling and formation to prepare the full battery for performance test, the first effect is 87.5 percent, and the cycle life is 96.3 percent in 500 weeks.
Example 3
1. Preparation of hydrophobic lithium battery cathode material
100g of NCA type lithium nickel cobalt aluminate are dispersed in 500mL of ethanol, and 0.04g of CH is added3(CH2)12-Si-OCH2CH3And uniformly mixing, filtering and drying to obtain the hydrophobic lithium battery cathode material.
2. Positive pole piece of hydrophobic lithium battery
2.1 homogenization: adding 40g of carbon tube slurry (5% of solid content), 20g of conductive carbon black and 500g of PVDF (polyvinylidene fluoride) glue solution (6%) into 2000g of the hydrophobic lithium battery anode material prepared in the step 1, stirring for half an hour by using a homogenizer at 15rpm, adding 500g of PVDF glue solution (6%) and 200mLNMP, and filtering the slurry by using a 200-mesh filter screen;
2.2 coating and rolling: coating the slurry on a 13-micron thick aluminum foil with an areal density of 15mg/cm2(ii) a And rolling the pole piece, wherein the thickness of the positive pole material is 45 mu m, and preparing the hydrophobic lithium battery positive pole.
2.3 the pole piece is subjected to the processes of sheet making, assembling and formation to prepare the full battery for performance test, the first effect is 86.8 percent, and the cycle life is 95.8 percent in 500 weeks.
Comparative example 1 conventional lithium battery positive electrode
1.1 homogenization: adding 40g of carbon tube slurry (5% of solid content), 20g of conductive carbon black and 500g of PVDF glue (6%) into 2000g of 811 type nickel cobalt lithium manganate, stirring for half an hour by using a homogenizer at 15rpm, adding 500g of PVDF glue (6%) and 200mLNMP, and filtering the slurry by using a 200-mesh filter screen;
1.2 coating and rolling: coating the slurry on a 13-micron thick aluminum foil with an areal density of 15mg/cm2(ii) a And rolling the pole piece, wherein the thickness of the positive pole material is 45 mu m, and preparing the hydrophobic lithium battery positive pole.
1.3 the pole piece is subjected to the processes of sheet making, assembling and formation to prepare a full battery for performance test, the first effect is 83.8 percent, and the cycle life is 92.8 percent in 500 weeks.
Experimental example 1 Performance test of lithium Battery cathode
1. Water absorption Performance test
The moisture of the positive pole piece is tested by using a Karl Fischer moisture meter under the test conditions of 150 ℃ and 100s, the moisture test result is shown in table 1, and the result shows that the hydrophobicity of the hydrophobically modified pole piece is obviously superior to that of an unmodified sample.
TABLE 1
| Moisture value 1(ppm) | Moisture value 2(ppm) | Moisture value 3(ppm) | Mean value of | |
| Example 1 | 53 | 60 | 43 | 52.0 |
| Example 2 | 43 | 48 | 52 | 47.7 |
| Example 3 | 62 | 68 | 65 | 65.0 |
| Comparative example 1 | 332 | 309 | 358 | 333.0 |
2. Electrolyte wettability detection
After rolling, 1mL of electrolyte (1.2mol/L LiPF6, EC/EMC/DMC system) was added dropwise to the surface of the positive electrode plate, and the electrolyte impregnation time was recorded, and the results are shown in Table 2. The test result shows that the wettability of the pole piece electrolyte subjected to hydrophobic modification is improved.
TABLE 2
| Soaking time 1(s) | Soaking time 2(s) | Soaking time 3(s) | Mean value of | |
| Example 1 | 2.8 | 2.5 | 2.6 | 2.6 |
| Example 2 | 2.9 | 2.5 | 2.4 | 2.6 |
| Example 3 | 1.9 | 1.8 | 2.1 | 1.9 |
| Comparative example 1 | 10.6 | 12.7 | 14.8 | 12.7 |
3. Electrode performance detection
The results of the formation first-effect and cycle life tests are shown in table 3, and the comparison of the performances of the pole pieces shows that the first-effect of the electrode subjected to hydrophobic modification is higher than 86 percent and is obviously higher than that of an unmodified sample; the capacity retention after 500 weeks cycling was greater than 95%, and also significantly better than the unmodified sample.
TABLE 3
| First wheel efficiency | Capacity retention rate of 500 weeks | |
| Example 1 | 86.6％ | 95.3％ |
| Example 2 | 87.5％ | 96.3％ |
| Example 3 | 86.8％ | 95.8％ |
| Comparative example 1 | 83.8％ | 92.8％ |
Claims (9)
1. The hydrophobic lithium battery positive electrode material is characterized in that a hydrophobic modifier is combined on the surface of a conventional lithium battery positive electrode material, wherein the molecular structure of the hydrophobic modifier is R-Xn(ii) a R is alkyl with 6-18 carbon atoms optionally having substituent selected from alkyl, aryl or alkoxy; x is-Si- (R)2)3OR1Or a carboxyl group, R1、R2Each is methyl or ethyl; n is 1, 2, 3 or 4.
2. The hydrophobic lithium battery positive electrode material of claim 1, wherein the conventional lithium battery positive electrode material is lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium cobalt oxide, or lithium nickel oxide.
3. The hydrophobic positive electrode material for lithium batteries according to claim 2, wherein the nickel cobalt lithium manganate is of type 111, 424, 523, 622, 711 or 811.
4. The hydrophobic lithium battery positive electrode material as claimed in any one of claims 1 to 3, wherein the mass ratio of the conventional lithium battery positive electrode material to the hydrophobic modifier is 1: 0.0001-0.1.
5. The method for preparing a positive electrode material for a hydrophobic lithium battery as claimed in any one of claims 1 to 4, comprising: dispersing the conventional lithium battery positive electrode material in a polar solvent, adding the hydrophobic modifier, uniformly mixing, filtering and drying to obtain the hydrophobic lithium battery positive electrode material.
6. The method of preparing the hydrophobic positive electrode material for a lithium battery according to claim 5, wherein the polar solvent is NMP, methanol, ethanol, propanol, isopropanol or water.
7. A hydrophobic lithium battery positive electrode, characterized in that the positive electrode material for a hydrophobic lithium battery according to any one of claims 1 to 4 is used for the positive electrode.
8. The method of preparing a hydrophobic lithium battery positive electrode as claimed in claim 7, comprising: homogenizing the hydrophobic lithium battery positive electrode material, and then coating the slurry on a positive electrode substrate to prepare the hydrophobic lithium battery positive electrode.
9. The method of preparing a hydrophobic lithium battery positive electrode as claimed in claim 7, comprising: homogenizing the positive electrode material of the conventional lithium battery, adding the hydrophobic modifier into the slurry, uniformly mixing to prepare hydrophobic positive electrode slurry, and then coating the slurry on a positive electrode substrate to prepare the hydrophobic lithium battery positive electrode.
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