CN113889595A - Preparation method of solid electrolyte coated graphite composite material - Google Patents
Preparation method of solid electrolyte coated graphite composite material Download PDFInfo
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- CN113889595A CN113889595A CN202010634581.XA CN202010634581A CN113889595A CN 113889595 A CN113889595 A CN 113889595A CN 202010634581 A CN202010634581 A CN 202010634581A CN 113889595 A CN113889595 A CN 113889595A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 93
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 84
- 239000010439 graphite Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 40
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims description 32
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000007833 carbon precursor Substances 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910020731 Li0.35La0.55TiO3 Inorganic materials 0.000 claims description 4
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910001323 Li2O2 Inorganic materials 0.000 claims description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 3
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 229910021384 soft carbon Inorganic materials 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 229910003002 lithium salt Inorganic materials 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 8
- -1 lithium salt compound Chemical class 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007770 graphite material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical compound [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 2
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 230000002427 irreversible effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GONRSTYRLCSFKI-UHFFFAOYSA-N C1(=O)OCC(C)OC(O1)=O.[Li] Chemical compound C1(=O)OCC(C)OC(O1)=O.[Li] GONRSTYRLCSFKI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
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- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
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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
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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
- H01M4/58—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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H01M2300/00—Electrolytes
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- H01M2300/0065—Solid electrolytes
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- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
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Abstract
The invention belongs to the field of secondary battery cathode materials, and particularly relates to a preparation method of a solid electrolyte coated graphite composite material. The solid electrolyte coated graphite composite material prepared by the method is of a core-shell structure, the core is graphite, the shell is of a double-layer structure consisting of a first shell and a second shell, and the first shell and the second shell are sequentially arranged from inside to outside; the first shell consists of a solid electrolyte, an organic lithium compound and amorphous carbon, wherein the mass ratio of the solid electrolyte to the organic lithium compound to the amorphous carbon is (50-80): (5-15): 1-5); the second shell is amorphous carbon; the thickness ratio of the inner core, the first shell and the second shell is as follows: 100 (1-10) and 0.5-2. Compared with the soft carbon-coated graphite composite material, the solid electrolyte-coated graphite composite material has the characteristics of high safety performance, high first-time efficiency, good rate capability, excellent cycle performance and the like.
Description
Technical Field
The invention belongs to the field of secondary battery cathode materials, and particularly relates to a preparation method of a solid electrolyte coated graphite composite material.
Background
At present, the negative electrode material of the commercial lithium ion battery mainly comprises graphite materials, the theoretical specific capacity of the graphite material as the negative electrode material is 372mAh/g, and the defects of poor charge-discharge rate performance, poor compatibility with electrolyte and the like exist, and the defects directly influence the application effect of the lithium ion battery in the fields of power and energy storage batteries.
In the prior art, the graphite material is subjected to coating modification treatment, for example, a soft carbon material is coated on the surface of the graphite material to improve the diffusion capacity of lithium ions in the material, so that the quick charging capacity of the graphite material is improved, but the problems of low diffusion speed, low lithium ion transmission rate, easy lithium precipitation caused by charging and discharging due to low interlayer spacing and the like still exist in the coating of the soft carbon material, so that the rate capability and the safety performance of the soft carbon coated graphite negative electrode material are still not satisfactory.
Disclosure of Invention
The invention aims to provide a preparation method of a solid electrolyte coated graphite composite material, which is used for improving the transmission rate of lithium ions in the charging and discharging process, inhibiting the growth and puncture of lithium dendrites and improving the multiplying power and safety performance of the composite material.
In order to achieve the purpose, the preparation method of the solid electrolyte coated graphite composite material adopts the technical scheme that:
a preparation method of a solid electrolyte coated graphite composite material comprises the following steps:
1) mixing a solid electrolyte, an amorphous carbon precursor, an organic lithium compound, an oxidant and a solvent to prepare a precursor mixed solution; the oxidant is Li2O2、LiNO3、LiNO2、Li2SO4、LiClO2One or more than two of the above; the mass ratio of the solid electrolyte, the amorphous carbon precursor, the organic lithium compound and the oxidant is (50-80): 1-5): 5-15): 1-5;
2) mixing the precursor mixed solution and graphite, spray-drying, carbonizing and crushing a spray-dried product to obtain first shell-coated graphite;
3) the first shell is coated with graphite and is coated with amorphous carbon.
The solid electrolyte coated graphite composite material prepared by the method is of a core-shell structure, the core is graphite, the shell is of a double-layer structure consisting of a first shell and a second shell, and the first shell and the second shell are sequentially arranged from inside to outside;
the first shell mainly comprises a solid electrolyte, an organic lithium compound and amorphous carbon, wherein the mass ratio of the solid electrolyte to the organic lithium compound to the amorphous carbon is (50-80): (5-15): 0.6-3);
the second shell is amorphous carbon;
the thickness ratio of the inner core, the first shell and the second shell is as follows: 100 (1-10) and 0.5-2.
The solid electrolyte coated graphite composite material prepared by the method improves the safety performance of the material by utilizing the characteristics of high ion conductivity and good structural stability of the solid electrolyte, and simultaneously utilizes the organic lithium compound to supplement lithium, so that the irreversible capacity of the material is reduced, and the first efficiency of the material is improved; further, the amorphous carbon is used for coating, so that the solid electrolyte can be prevented from directly contacting with the electrolyte, the probability of side reaction between metal elements in the solid electrolyte and the electrolyte is reduced, and the cycle performance of the battery is improved by using the conductivity of the amorphous carbon. Compared with the soft carbon-coated graphite composite material, the solid electrolyte-coated graphite composite material has the characteristics of high safety performance, high first-time efficiency, good rate capability, excellent cycle performance and the like.
The preparation method of the solid electrolyte coated graphite composite material provided by the invention is simple in preparation process and suitable for industrial production.
In order to further improve the coating uniformity of the first shell, the mass concentration of the precursor mixed solution is preferably (1-5)%, and the mass ratio of the precursor mixed solution to the graphite is preferably (100-300). In the step 1), the amorphous carbon precursor is one of polyvinylidene fluoride and polyethylene oxide. The shell made of the amorphous carbon precursor has certain plasticity, is beneficial to forming the solid electrolyte with higher hardness and uniformly coats the solid electrolyteThe graphite surface. In the step, the action of the oxidant is mainly to carry out ring-opening reaction on the organic lithium salt compound, and then carboxyl in the organic lithium compound reacts with groups on the surface of the solid electrolyte to generate a compound with a stable structure. Such as lithium difluoro (oxalato) borate, under the condition of an oxidant, the lithium difluoro (oxalato) borate is subjected to chain opening to generate-COOH groups, and Li is taken as the solid electrolyte1.3Al0.3Ti1.7(PO4)3Al in (1)3+、Ti4+And the combination is chemically reacted to finally generate the crosslinking compound.
The carbonization process in the step 2) can fully convert the amorphous carbon precursor into amorphous carbon, and preferably, the carbonization temperature in the step 2) is 700-1000 ℃. The carbonization time is 6-24 h.
With reference to the existing amorphous carbon coating technology, preferably, in step 3), the amorphous carbon coating is performed by performing vapor deposition on the graphite coated by the first shell by using a carbon source gas, wherein the temperature of the vapor deposition is (700-1000) ° c, and the time is (1-6) h. The amorphous carbon prepared by the vapor deposition method has the characteristic of large specific surface area, can improve the liquid absorption and retention capacity of the material, and is beneficial to the improvement of rate capability and cycle performance.
In order to further improve the vapor deposition efficiency, preferably, in step 3), the carbon source gas is one or more of methane, acetylene and ethylene.
In order to further improve the tap density of the negative electrode material and increase the energy density of the battery, the particle size of the solid electrolyte coated graphite composite material is preferably 8-18 μm.
Preferably, the solid electrolyte is Li1.3Al0.3Ti1.7(PO4)3，Li7La3Zr2O12、Li0.35La0.55TiO3One or more than two of them. The solid electrolyte has the characteristics of high lithium ion conductivity, chemical stability, wide electrochemical window and high strength and hardness, and can effectively inhibit dendritic crystal growth and puncture and improve safety performance. The above solid electrolyte is coated on the graphite surfaceThe quick charging performance and the safety performance of the cathode material can be obviously improved.
Preferably, the organic lithium compound is one or more of lithium bistrifluoromethylsulfonyl imide, lithium difluorooxalato borate, azobenzene 4, 4-dicarboxylic acid lithium salt, lithium methoxide, lithium ethoxide, lithium formate, lithium oxalate and lithium stearate. The solid electrolyte and the organic lithium compound are respectively inorganic lithium salt and organic lithium salt, so that the synergistic effect between the inorganic lithium salt and the organic lithium salt can be exerted, and the SEI formation quality (the compactness and the stability of the material) can be improved, thereby improving the cycle performance of the material.
Drawings
Fig. 1 is an SEM image of the solid electrolyte-coated graphite composite material prepared in example 1.
Detailed Description
The following examples are provided to further illustrate the practice of the invention. In the following examples, the amorphous carbon precursor polyvinylidene fluoride has a melting point of 170-200 ℃ and a molecular weight of 30-60 ten thousand; the melting point of the polyethylene oxide is 120-140 ℃, and the molecular weight is 30-50 ten thousand.
First, a specific example of the method for preparing the solid electrolyte coated graphite composite material of the present invention
Example 1
The solid electrolyte coated graphite composite material of the embodiment has a core-shell structure, the particle size is (8-18) mu m, the core is graphite, the shell is a double-shell structure consisting of a first shell and a second shell, the first shell and the second shell are sequentially arranged from inside to outside, and the first shell consists of a solid electrolyte, an organic lithium compound and amorphous carbon. The second shell is amorphous carbon. The thickness ratio of the inner core to the first shell to the second shell is 100:5: 1.
In the first case, the solid electrolyte is Li1.3Al0.3Ti1.7(PO4)3The organic lithium compound is lithium difluoro oxalate borate, the amorphous carbon is formed by pyrolysis of polyvinylidene fluoride, and the mass ratio of the solid electrolyte, the organic lithium compound and the amorphous carbon is 67:10: 1.
In the second enclosure, amorphous carbon is formed by vapor deposition of a carbon source gas.
The preparation method of the solid electrolyte coated graphite composite material of the embodiment comprises the following steps:
1) preparing a precursor solution:
10g of lithium difluorooxalato borate and 3g of polyvinylidene fluoride were added to 1000ml of N-methylpyrrolidone and mixed well, and then 67g of Li was added1.3Al0.3Ti1.7(PO4)3Solid electrolyte powder, 3g Li2O2Adding 1666ml of N-methyl pyrrolidone organic solvent into the oxidant to prepare precursor mixed liquor with the mass concentration of 3%;
2) precursor material of graphite composite material coated by solid electrolyte:
adding 200g of artificial graphite into 100g of precursor mixed solution, uniformly dispersing by a ball mill, carrying out spray drying, heating to 800 ℃ at a heating rate of 5 ℃/min under an argon inert atmosphere, keeping the temperature for 12h, naturally cooling to room temperature, and crushing to obtain a solid electrolyte coated graphite composite material precursor material (namely, first shell coated graphite);
3) solid electrolyte coated graphite composite material:
transferring the graphite composite material precursor material coated by the solid electrolyte into a tubular furnace, firstly introducing argon inert gas to exhaust air in the tube, then introducing methane carbon source gas, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, then stopping introducing the carbon source gas, introducing argon inert gas, and naturally cooling to room temperature to obtain the graphite composite material coated by the solid electrolyte.
Example 2
The solid electrolyte coated graphite composite material of the embodiment has a core-shell structure, the particle size is (8-18) mu m, the core is graphite, the shell is a double-shell structure consisting of a first shell and a second shell, the first shell and the second shell are sequentially arranged from inside to outside, and the first shell consists of a solid electrolyte, an organic lithium compound and amorphous carbon. The second shell is amorphous carbon. The thickness ratio of the inner core to the first shell to the second shell is 100:1: 0.5.
In the first case, the solid electrolyte is Li7La3Zr2O12The organic lithium compound is azobenzene 4, 4-dicarboxylic acid lithium salt, the amorphous carbon is formed by polyethylene oxide pyrolysis, and the mass ratio of the solid electrolyte, the organic lithium compound and the amorphous carbon is 50:5: 0.6.
In the second enclosure, amorphous carbon is formed by vapor deposition of a carbon source gas.
The preparation method of the solid electrolyte coated graphite composite material of the embodiment comprises the following steps:
1) preparing a precursor solution:
5g of azobenzene 4, 4-dicarboxylic acid lithium salt and 1g of polyethylene oxide were added to 2000ml of N-methylpyrrolidone, mixed uniformly, and then 50g of Li was added7La3Zr2O12Solid electrolyte powder, 1g LiNO3Adding 4666ml of N-methyl pyrrolidone organic solvent into the oxidant to prepare precursor mixed liquid with the mass concentration of 1%;
2) precursor material of graphite composite material coated by solid electrolyte:
weighing 100g of precursor mixed solution, adding 100g of artificial graphite, uniformly dispersing by a ball mill, performing spray drying, heating to 700 ℃ at a heating rate of 1 ℃/min under an argon inert atmosphere, preserving heat for 24h, naturally cooling to room temperature, and crushing to obtain a solid electrolyte-coated graphite composite material precursor material;
3) solid electrolyte coated graphite composite material:
transferring the graphite composite material precursor material coated with the solid electrolyte into a tubular furnace, firstly introducing argon inert gas to exhaust air in the tube, then introducing ethylene carbon source gas, heating to 700 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 6h, then stopping introducing the ethylene carbon source gas, introducing argon inert gas, and naturally cooling to room temperature to obtain the graphite composite material coated with the solid electrolyte (the residual carbon content of amorphous carbon in the embodiment is 60%, and the same is carried out in the following embodiments).
Example 3
The solid electrolyte coated graphite composite material of the embodiment has a core-shell structure, the particle size is (8-18) mu m, the core is graphite, the shell is a double-shell structure consisting of a first shell and a second shell, the first shell and the second shell are sequentially arranged from inside to outside, and the first shell consists of a solid electrolyte, an organic lithium compound and amorphous carbon. The second shell is amorphous carbon. The thickness ratio of the inner core to the first shell to the second shell is 100:10: 2.
In the first case, the solid electrolyte is Li0.35La0.55TiO3The organic lithium compound is lithium stearate, the amorphous carbon is formed by pyrolysis of polyvinylidene fluoride, and the mass ratio of the solid electrolyte, the organic lithium compound and the amorphous carbon is 80:15: 3.
In the second enclosure, amorphous carbon is formed by vapor deposition of a carbon source gas.
The preparation method of the solid electrolyte coated graphite composite material of the embodiment comprises the following steps:
1) preparing a precursor solution:
15g of lithium propylene dicarbonate and 5g of polyvinylidene fluoride were added to 2000ml of N-methylpyrrolidone, and mixed uniformly, followed by addition of 80g of Li0.35La0.55TiO3Solid electrolyte powder, 5g Li2SO4Adding 3250ml of N-methyl pyrrolidone into an oxidant to prepare a precursor mixed solution with the mass concentration of 5%;
2) precursor material of graphite composite material coated by solid electrolyte:
taking 100g of precursor mixed solution, adding 300g of artificial graphite, uniformly dispersing by a ball mill, carrying out spray drying, heating to 1000 ℃ at a heating rate of 10 ℃/min under an argon inert atmosphere, keeping the temperature for 6h, naturally cooling to room temperature, and crushing to obtain a graphite composite material precursor material coated by a solid electrolyte;
3) solid electrolyte coated graphite composite material:
transferring the graphite composite material precursor material coated by the solid electrolyte into a tubular furnace, firstly introducing argon inert gas to exhaust air in the tube, then introducing acetylene carbon source gas, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, then stopping introducing the acetylene carbon source gas, introducing argon inert gas, and naturally cooling to room temperature to obtain the graphite composite material coated by the solid electrolyte.
Second, comparative example
Comparative example 1
Dissolving 5g of asphalt in 100ml of N-methyl pyrrolidone, adding 100g of artificial graphite after uniform dissolution, then adding 400ml of N-methyl pyrrolidone, after uniform dispersion, spray drying, then heating to 800 ℃ at a heating rate of 5 ℃/min under an argon inert atmosphere, then naturally cooling to room temperature, and crushing to obtain the graphite composite material coated with the asphalt.
Comparative example 2
1) Preparing a precursor solution:
10g of lithium difluorooxalato borate and 67g of Li1.3Al0.3Ti1.7(PO4)3Adding 2000ml of N-methyl pyrrolidone organic solvent into solid electrolyte powder to prepare precursor mixed liquid with the mass concentration of 3%;
2) precursor material of graphite composite material coated by solid electrolyte:
adding 200g of artificial graphite into 100g of precursor mixed solution, uniformly dispersing by a ball mill, carrying out spray drying, heating to 800 ℃ at a heating rate of 5 ℃/min under an argon inert atmosphere, keeping the temperature for 12h, naturally cooling to room temperature, and crushing to obtain a graphite composite material precursor material coated by a solid electrolyte;
3) solid electrolyte coated graphite composite material:
transferring the graphite composite material precursor material coated by the solid electrolyte into a tubular furnace, firstly introducing argon inert gas to exhaust air in the tube, then introducing methane carbon source gas, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, then stopping introducing the carbon source gas, introducing argon inert gas, and naturally cooling to room temperature to obtain the graphite composite material coated by the solid electrolyte.
Third, Experimental example
Experimental example 1 test of physical and chemical Properties
1.1SEM test
The graphite composite material prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 1. As can be seen from the figure, the graphite composite material is in an irregular particle shape, and the particle size is between (8-18) mu m.
1.2 powder conductivity test
The graphite composite materials in examples 1 to 3 and comparative examples 1 to 2 were subjected to a powder conductivity test, which was carried out by the following method: pressing the powder into a blocky structure on a powder compaction density instrument under the pressure of 2T, and then testing the powder conductivity by adopting a four-probe tester. The test results are shown in table 1.
1.3 tap Density test
The tap density was tested according to GB/T2433and 2009 graphite-type cathode materials for lithium ion batteries, and the test results are shown in Table 1.
TABLE 1 physicochemical Properties of graphite composite materials in examples and comparative examples
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Conductivity (S/cm) | 4.23 | 4.18 | 4.11 | 0.84 | 2.1 |
| Tap density (g/cm)3) | 1.14 | 1.11 | 1.08 | 0.92 | 0.97 |
As can be seen from table 1, the conductivity of the solid electrolyte-coated graphite composite material prepared by the present invention is significantly higher than that of the comparative example, because: the surface of the material is coated with the solid electrolyte with higher conductivity, so that the transmission rate of electrons is improved; meanwhile, the compact carbon layer on the outermost layer is also beneficial to improving the electronic conductivity of the material; meanwhile, the solid electrolyte coated on the surface of the material has the characteristics of high density, high density and the like, so that the tap density of the material is improved.
Experimental example 2 button cell test
The graphite materials of examples 1-3 and comparative example were assembled into button cells a1, a2, A3, B1, B2, respectively. The assembling method comprises the following steps: and adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on copper foil, and drying and rolling to obtain the negative electrode plate. The binder used was LA132 binder, the conductive agent was SP, the negative electrode materials were the graphite composite materials in examples 1 to 3 and comparative example, respectively, and the solvent was secondary distilled water. The proportion of each component is as follows: and (3) anode material: SP: LA 132: 95g of secondary distilled water: 1 g: 4 g: 220 mL; the electrolyte is LiPF6/EC+DEC(LiPF6The concentration of the lithium ion battery is 1.2mol/L, the volume ratio of EC to DEC is 1:1), the metal lithium sheet is used as a counter electrode, and the diaphragm is a Polyethylene (PE), polypropylene (PP) or polyethylene propylene (PEP) composite membrane. Button cell assembled in hydrogen charging gasThe electrochemical performance test is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.005V to 2.0V, and the charging and discharging multiplying power is 0.1C. The test results are shown in table 2.
Table 2 comparison of performance of lithium ion batteries prepared from graphite materials of examples 1-3 and comparative example 1
As can be seen from table 2, the first discharge capacity and the first charge-discharge efficiency of the lithium ion battery using the composite negative electrode materials obtained in examples 1 to 3 are significantly higher than those of the comparative example, because: the graphite surface is coated with the solid electrolyte composite material, the lithium ion intercalation and deintercalation are promoted by utilizing the high conductivity of the solid electrolyte lithium ions, and meanwhile, the solid electrolyte and the organic lithium compound are respectively inorganic lithium salt and organic lithium salt, so that the formation quality of an SEI film is improved, the irreversible capacity loss of the material is reduced, and the primary efficiency is improved.
Experimental example 3 pouch cell test
The graphite composite materials in examples 1 to 3 and comparative example were used as negative electrode materials to prepare negative electrode sheets. With ternary materials (LiNi)1/3Co1/3Mn1/3O2) As the positive electrode, LiPF6Solution (solvent EC + DEC, volume ratio 1:1, LiPF)6Concentration of 1.3mol/L) is used as electrolyte, celegard2400 is used as a diaphragm, and 5Ah soft package batteries A1, A2, A3, B1 and B2 are prepared. And testing the cycle performance and the rate performance of the soft package battery.
Cycle performance test conditions: the charging and discharging current is 1C/1C, the voltage range is 2.8-4.2V, and the cycle times are 500 times.
Multiplying power performance test conditions: charging rate: 1C/3C/5C/8C, discharge multiplying power of 1C; voltage range: 2.8-4.2V.
The test results are shown in tables 3 and 4.
Table 3 comparison of cycle performance of lithium ion batteries prepared from graphite composites of examples 1-3 and comparative examples
As can be seen from table 3, the cycle performance of the pouch battery prepared from the graphite composite material of the present invention is superior to that of the comparative example, because the solid electrolyte and lithium salt on the surface of graphite improve the transmission rate of lithium ions in the aspect of 1C/1C rate cycle performance; meanwhile, the circulation performance of the solid electrolyte is improved by utilizing the characteristic of stable structure of the solid electrolyte.
Table 4 multiplying power charging performance comparison table
As can be seen from table 4, the soft package battery prepared from the graphite composite material of the present invention has a better constant current ratio, and the reason is that the surface of the material in the embodiment is coated with the solid electrolyte and the lithium salt, which can improve the insertion and extraction rate of lithium ions in the rate charging process of the material, thereby improving the rate charging performance of the material.
And (4) safety performance testing:
needle short circuit test: the lithium ion batteries prepared in examples 1-3 and comparative examples 1-2 were tested according to the UL2054 safety standard, and the results are shown in Table 5 below.
Table 5 safety performance test of each example and comparative example
As can be seen from table 5, the lithium ion batteries using the materials of examples 1-3 have a high safety factor and a lower temperature rise relative to the comparative examples. The reason is that: the solid electrolyte coated graphite composite material has high-temperature resistance, reduces the occurrence probability of thermal runaway in the short circuit process of a battery, and improves the safety performance of the battery.
Claims (8)
1. The preparation method of the solid electrolyte coated graphite composite material is characterized by comprising the following steps:
1) mixing a solid electrolyte, an amorphous carbon precursor, an organic lithium compound, an oxidant and a solvent to prepare a precursor mixed solution; the oxidant is Li2O2、LiNO3、LiNO2、Li2SO4、LiClO2One or more than two of the above; the mass ratio of the solid electrolyte, the amorphous carbon precursor, the organic lithium compound and the oxidant is (50-80): 1-5): 5-15): 1-5;
2) mixing the precursor mixed solution and graphite, spray-drying, carbonizing and crushing a spray-dried product to obtain first shell-coated graphite;
3) the first shell is coated with graphite and is coated with amorphous carbon.
2. The method for producing a solid electrolyte-coated graphite composite material according to claim 1, wherein the mass concentration of the precursor mixture is (1 to 5)%, and the mass ratio of the precursor mixture to graphite is 100 (100 to 300).
3. The method of preparing the solid electrolyte-coated graphite composite material according to claim 1, wherein the carbonization temperature in the step 2) is (700 to 1000 ℃).
4. The method for preparing the solid electrolyte coated graphite composite material according to claim 1, wherein in the step 3), the amorphous carbon is coated by performing vapor deposition on the first shell coated graphite by using a carbon source gas, the temperature of the vapor deposition is (700-1000) DEG C, and the time is (1-6) h.
5. The method of preparing the solid electrolyte-coated graphite composite material according to claim 4, wherein the carbon source gas is one or more of methane, acetylene, and ethylene.
6. The method for producing a solid electrolyte-coated graphite composite material according to any one of claims 1 to 5, wherein in step 1), the amorphous carbon precursor is one of polyvinylidene fluoride and polyethylene oxide.
7. The method for producing a solid electrolyte-coated graphite composite material according to any one of claims 1 to 5, wherein in step 1), the solid electrolyte is Li1.3Al0.3Ti1.7(PO4)3，Li7La3Zr2O12、Li0.35La0.55TiO3One or more than two of them.
8. The method for preparing a solid electrolyte-coated graphite composite material according to any one of claims 1 to 5, wherein in step 1), the organic lithium compound is one or more of lithium bistrifluoromethylsulfonyl imide, lithium difluorooxalato borate, lithium azobenzene 4, 4-dicarboxylate, lithium methoxide, lithium ethoxide, lithium formate, lithium oxalate and lithium stearate.
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