CN115954465A - High-power hard carbon composite material and preparation method thereof - Google Patents
High-power hard carbon composite material and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 14
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical group [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- -1 stirring and pulping Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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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
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- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery materials, and provides a high-power hard carbon composite material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, adding resin into organic alcohol for dissolving, and then adding inorganic ferric salt to obtain a suspension A; s2, adding ammonium fluoride into the graphene oxide solution, and uniformly dispersing to obtain a solution B; s3, adding the solution B into the suspension A, heating to 50-100 ℃, adding a cross-linking agent, and introducing oxidizing gas to obtain a mixture C; and S4, drying the mixture C and then carbonizing to obtain the high-power hard carbon composite material. Through the technical scheme, the problem that the power performance, the first efficiency and the cycle performance of hard carbon in the prior art are poor is solved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a high-power hard carbon composite material and a preparation method thereof.
Background
Carbon materials are the inevitable choice of negative electrode materials due to their abundant reserves, excellent electrical conductivity and good cycling stability. Carbon materials can be generally classified into graphitic materials (natural graphites and modified graphites) and amorphous hard carbons and soft carbons according to the difference in the degree of graphitization of the carbon materials.
The hard carbon material is applied to the fields of HEV and the like due to the advantages of low expansion, excellent low-temperature performance, wide material source and the like, but the popularization and the application of the hard carbon material in the fields of EV and the like are limited due to the low first efficiency and the normal-temperature power performance deviation.
The method for improving the first efficiency of the material is to coat soft carbon on the surface of the material, and although the first efficiency can be improved, the power performance of the material can be reduced; if the power performance of the material can be improved by reducing the particle size or doping metal elements, the energy density is reduced. Therefore, by means of doping and coating, the energy density and the first efficiency can be improved, and the power performance of the material can be improved.
Disclosure of Invention
The invention provides a high-power hard carbon composite material and a preparation method thereof, and solves the problems of poor power performance, first efficiency and cycle performance of hard carbon in the prior art.
The technical scheme of the invention is as follows:
a preparation method of a high-power hard carbon composite material comprises the following steps:
s1, adding resin into organic alcohol for dissolving, and then adding inorganic ferric salt to obtain a suspension A;
s2, adding ammonium fluoride into the graphene oxide solution, and uniformly dispersing to obtain a solution B;
s3, adding the solution B into the suspension A, heating to 50-100 ℃, adding a cross-linking agent, and introducing oxidizing gas to obtain a mixture C;
and S4, drying the mixture C and then carbonizing to obtain the high-power hard carbon composite material.
As a further technical scheme, the resin comprises one or more of epoxy resin, phenolic resin and furfural resin.
As a further technical scheme, the organic alcohol comprises one or more of butanediol, ethylene glycol, glycerol, n-butanol and benzyl alcohol.
As a further technical scheme, the valence of iron in the inorganic iron salt is trivalent.
As a further technical scheme, the inorganic iron salt is one or more of ferric sulfate, ferric nitrate and ferric chloride.
As a further technical scheme, the mass ratio of the resin, the organic alcohol and the inorganic iron salt is 100:500-2000:1-10.
As a further technical solution, at least one of the following technical features is also included:
the graphene oxide solution is an N-methyl pyrrolidone solution of graphene oxide;
the concentration of the graphene oxide is 1-5wt%;
the mass ratio of the ammonium fluoride to the graphene oxide is 1-10:0.5-2.
As a further technical solution, at least one of the following technical features is also included:
the mass ratio of the cross-linking agent to the resin is 5-20:100, respectively;
the cross-linking agent is one of furfural, benzaldehyde, trioxymethylene and formaldehyde.
As a further technical scheme, the oxidizing gas is one of chlorine, bromine, oxygen and hydrogen peroxide.
As a further technical scheme, the addition amount of the suspension A and the solution B is based on the following standard: fe 3+ And F - In a molar ratio of 1.
As a further technical scheme, the carbonization temperature is 800-1200 ℃, and the time is 1-6h.
As a further technical scheme, the airflow rate of the oxidizing gas is 10-100mL/min, and the flowing-in time is 30-300min.
The high-power hard carbon composite material is prepared by the preparation method and consists of hard carbon and ferric fluoride doped in the hard carbon, wherein the mass ratio of the ferric fluoride accounts for 1-10wt% of the total amount of the composite material.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the ferric fluoride is doped in the hard carbon, so that on one hand, the impedance is reduced by utilizing the high specific capacity and high electronic conductivity of the ferric fluoride, and on the other hand, the ferric fluoride has good compatibility with the electrolyte, and the high-temperature storage performance can be improved.
2. Inorganic iron salt is uniformly mixed in the hard carbon precursor by adopting a liquid phase method, so that the impedance is reduced; meanwhile, the fluoride is doped in the graphene oxide solution, and the agglomeration of the fluoride is avoided by virtue of a lamellar structure of graphene; meanwhile, a cross-linking agent and oxidizing gas are added for surface treatment, holes are formed in the hard carbon, the lithium storage capacity is improved, the defects on the surface of the material are reduced by means of the oxidizing gas, and the primary efficiency is improved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is an SEM image of an iron fluoride-doped hard carbon composite prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
A preparation method of a high-power hard carbon composite material comprises the following steps:
s1, adding 100g of phenolic resin into 1000g of glycerol for dissolving, and then adding 5g of ferric sulfate (0.0125 mol) to obtain a suspension A;
s2, adding 1.85g of ammonium fluoride (0.05 mol) into 40g of N-methylpyrrolidone solution of graphene oxide with the concentration of 3wt% to be uniformly dispersed to obtain a solution B;
s3, adding the solution B obtained in the step S2 into the suspension A obtained in the step S1, heating to 80 ℃, stirring for 3 hours, adding 10g of furfural, introducing chlorine gas at an airflow rate of 50mL/min for 60 minutes, and filtering to obtain a mixture C;
and S4, drying the mixture C in vacuum at 80 ℃ for 24h, and carbonizing at 900 ℃ for 3h to obtain the ferric fluoride doped hard carbon composite material.
Example 2
A preparation method of a high-power hard carbon composite material comprises the following steps:
s1, adding 100g of furfural resin into 500g of glycerol for dissolution, and then adding 1g of ferric nitrate (0.0041 mol) to obtain a suspension A;
s2, adding 0.7585g of ammonium fluoride (0.0205 mol) into 37.9g of N-methylpyrrolidone solution of graphene oxide with the concentration of 1wt% to be uniformly dispersed to obtain a solution B;
s3, adding the solution B obtained in the S2 into the suspension A obtained in the S1, heating to 50 ℃, stirring for 3 hours, adding 5g of benzaldehyde, introducing bromine gas at an airflow rate of 10mL/min for 300 minutes, and filtering to obtain a mixture C;
and S4, drying the mixture C in vacuum at 80 ℃ for 24h, and carbonizing at 800 ℃ for 6h to obtain the ferric fluoride doped hard carbon composite material.
Example 3
A preparation method of a high-power hard carbon composite material comprises the following steps:
s1, adding 100g of epoxy resin into 2000g of benzyl alcohol for dissolving, and then adding 10g of ferric chloride (0.062 mol) to obtain suspension A;
s2, adding 6.85g of ammonium fluoride (0.186 mol) into 40g of N-methylpyrrolidone solution of 5wt% graphene oxide to be uniformly dispersed to obtain solution B;
s3, adding the solution B obtained in the S2 into the suspension A obtained in the S1, heating to 100 ℃, stirring for 3 hours, adding 20g of trioxymethylene, introducing oxygen gas at an airflow rate of 100mL/min for 30 minutes, and filtering to obtain a mixture C;
and S4, drying the mixture C in vacuum at 80 ℃ for 24h, and carbonizing at 1200 ℃ for 1h to obtain the ferric fluoride doped hard carbon composite material.
Comparative example 1
Stirring 100g of phenolic resin and 10g of N-methylpyrrolidone solution of graphene oxide with the concentration of 1wt% at the temperature of 80 ℃ for 3h, then adding 10g of furfural, stirring for 3h, then filtering, vacuum-drying at the temperature of 80 ℃ for 24h, then transferring the obtained material to a tubular furnace, and carbonizing at the temperature of 900 ℃ for 3h to obtain the graphene doped hard carbon composite material.
Comparative example 2
A preparation method of a high-power hard carbon composite material comprises the following steps:
s1, adding 100g of phenolic resin into 1000g of glycerol for dissolving, and then adding 5g of ferric sulfate (0.0125 mol) to obtain a suspension A;
s2, adding 1.85g of ammonium fluoride (0.05 mol) into the suspension A obtained in the S1, heating to 80 ℃, stirring for 3 hours, adding 10g of furfural, introducing chlorine gas at an airflow rate of 50mL/min for 60 minutes, and filtering to obtain a mixture C;
and S3, drying the mixture C in vacuum at 80 ℃ for 24h, and carbonizing at 900 ℃ for 3h to obtain the ferric fluoride doped hard carbon composite material.
Comparative example 3
A preparation method of a high-power hard carbon composite material comprises the following steps:
s1, adding 100g of phenolic resin into 1000g of glycerol for dissolving, and then adding 5g of ferric sulfate (0.0125 mol) to obtain a suspension A;
s2, adding 1.85g of ammonium fluoride (0.05 mol) into 40g of N-methylpyrrolidone solution of graphene oxide with the concentration of 3wt% to be uniformly dispersed to obtain a solution B;
s3, adding the solution B obtained in the step S2 into the suspension A obtained in the step S1, uniformly stirring, introducing chlorine gas at an airflow rate of 50mL/min for 60min, and filtering to obtain a mixture C;
and S4, drying the mixture C in vacuum at 80 ℃ for 24h, and carbonizing at 900 ℃ for 3h to obtain the ferric fluoride doped hard carbon composite material.
Comparative example 4
The procedure of example 1 was repeated except that ammonia fluoride was replaced with an equimolar amount of sodium fluoride as compared with example 1.
The test method comprises the following steps:
1. SEM test
The SEM test of the iron fluoride-doped hard carbon composite material prepared in the example 1 is shown in figure 1, and it can be seen from the figure that the hard carbon material prepared in the example 1 has a spheroidal structure, uniform size distribution and a particle size of 5-15 mu m.
2. Physicochemical Properties and button cell test
The hard carbon composite materials prepared in examples and comparative examples were subjected to particle size, tap density, specific surface area, elemental analysis, and specific capacity tests thereof. The test method comprises the following steps: GB/T-243358-2019 graphite cathode material for lithium ion batteries.
Hard carbon composite materials obtained in examples 1-3 and comparative example are respectively assembled into button cells A1, A2, A3 and B1; the preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the copper foil to obtain the copper-clad laminate. The binder used is LA132 binder, conductive agent SP, the negative electrode material is the hard carbon material prepared in the examples and the comparative examples respectively, the solvent is secondary distilled water, and the proportion is as follows: and (3) anode material: SP: LA132: double distilled water =95g:1g:4g:220mL, and preparing a negative pole piece; the electrolyte is LiPF 6 The battery is characterized in that the battery comprises a counter electrode and a metal lithium sheet, wherein the counter electrode is EC + DEC (volume ratio is 1. The multiplying power (2C/0.1C) and the cycle performance (0.2C/0.2C, 200 times) of the button cell battery are tested at the same time, and the test results are shown in table 1.
Table 1 physicochemical properties of composite materials and button cell test results obtained in examples and comparative examples
As can be seen from table 1, the first discharge capacity and the first efficiency, rate capability and cycle capability of the hard carbon composite material prepared in the example were significantly improved as compared to the comparative example, because the hard carbon composite material according to the present invention contains iron fluoride and reduces the impedance to improve the rate capability depending on its high specific capacity and its high electronic conductivity. Meanwhile, the lithium storage capacity is improved by adding the cross-linking agent and performing surface treatment on the oxidizing gas of the cross-linking agent, holes are formed in the hard carbon, the defects on the surface of the material are reduced by the oxidizing gas, and the first efficiency is improved.
3. Testing the high-temperature storage performance of the soft package battery:
the hard carbon composite materials in the examples and the comparative examples are used as negative electrodes, and are subjected to slurry mixing and coating to prepare negative electrode plates made of ternary materials (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) As the positive electrode, liPF 6 (the solvent is EC + DEC, the volume ratio is 1.
The capacity of the battery in a full-charge state is X when the battery is tested at 60 DEG C 1 Then placed at 60 ℃ for 30 days, and then tested again for the capacity X of the battery 2 Calculating charge retention = X 2 /X 1 *100 percent; after that, the battery was fully charged (100% SOC), and the capacity of the battery was tested to X 3 Calculating recovery capacity = X 3 /X 1 *100 percent; the results are shown in Table 2.
Table 2 high temperature storage performance test of pouch cells prepared from composite materials of examples and comparative examples
As can be seen from table 2, the high temperature storage performance of the example material is superior to that of the comparative example because the ferric fluoride has better compatibility with the electrolyte, and the high temperature storage performance is improved.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-power hard carbon composite material is characterized by comprising the following steps:
s1, adding resin into organic alcohol for dissolving, and then adding inorganic ferric salt to obtain a suspension A;
s2, adding ammonium fluoride into the graphene oxide solution, and uniformly dispersing to obtain a solution B;
s3, adding the solution B into the suspension A, heating to 50-100 ℃, adding a cross-linking agent, and introducing oxidizing gas to obtain a mixture C;
and S4, drying the mixture C and carbonizing to obtain the high-power hard carbon composite material.
2. The method for preparing high power hard carbon composite material according to claim 1, wherein the resin comprises one or more of epoxy resin, phenolic resin and furfural resin.
3. The method for preparing high-power hard carbon composite material according to claim 1, wherein the valence of iron in the inorganic iron salt is trivalent.
4. The preparation method of the high-power hard carbon composite material according to claim 3, wherein the inorganic ferric salt is one or more of ferric sulfate, ferric nitrate and ferric chloride.
5. The preparation method of the high-power hard carbon composite material according to claim 1, wherein the mass ratio of the resin to the organic alcohol to the inorganic iron salt is 100:500-2000:1-10.
6. The method for preparing a high power hard carbon composite material according to claim 1, further comprising at least one of the following technical features:
the graphene oxide solution is an N-methyl pyrrolidone solution of graphene oxide;
the concentration of the graphene oxide is 1-5wt%;
the mass ratio of the ammonium fluoride to the graphene oxide is 1-10:0.5-2.
7. The method for preparing a high power hard carbon composite material according to claim 1, further comprising at least one of the following technical features:
the mass ratio of the cross-linking agent to the resin is 5-20:100, respectively;
the cross-linking agent is one of furfural, benzaldehyde, trioxymethylene and formaldehyde.
8. The method for preparing the high-power hard carbon composite material according to claim 1, wherein the oxidizing gas is one of chlorine, bromine, oxygen and hydrogen peroxide.
9. The preparation method of the high-power hard carbon composite material according to claim 1, wherein the addition amounts of the suspension A and the solution B are based on the following standards: fe 3+ And F - In a molar ratio of 1.
10. A high-power hard carbon composite material, which is obtained by the preparation method of any one of claims 1 to 9 and consists of hard carbon and ferric fluoride doped in the hard carbon, wherein the mass ratio of the ferric fluoride accounts for 1 to 10wt% of the total weight of the composite material.
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Effective date of registration: 20231222 Address after: 653100 Longquan District, high tech Zone, Yuxi City, Yunnan Province (Sanjie community, Dajie street, Jiangchuan District) Patentee after: Yunnan Kuntian New Energy Co.,Ltd. Address before: 050000 No. 8, kuntian Avenue, Suyang Township, Yuanshi County, Shijiazhuang City, Hebei Province Patentee before: Hebei kuntian new energy Co.,Ltd. |