CN115172710A - Iron oxide graphite composite material for lithium ion battery and preparation method thereof - Google Patents
Iron oxide graphite composite material for lithium ion battery and preparation method thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 53
- 239000010439 graphite Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000002506 iron compounds Chemical class 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 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
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 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 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 229910021383 artificial graphite Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000007600 charging Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 235000014413 iron hydroxide Nutrition 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an iron oxide graphite composite material for a lithium ion battery and a preparation method thereof. Adding a conductive agent and an alkaline solution thereof into an iron-containing inorganic compound solution, and sintering to obtain porous iron oxide through codeposition reaction; dissolving the porous ferric oxide in a resin solution, adding graphite, and performing ball milling and carbonization to obtain the iron-based composite material. The invention can improve the power performance and energy density of graphite and give consideration to the storage and expansion performance of the material.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, particularly relates to an iron oxide graphite composite material for a lithium ion battery, and also relates to a preparation method of the iron oxide graphite composite material for the lithium ion battery.
Background
The current marketable negative electrode material mainly takes artificial graphite and natural graphite as main materials, and has the defects of low energy density and the like (the artificial graphite is about 360mAh/g, and the compaction density is less than or equal to 1.7g/cm < 3 >). In recent years, transition metal oxides, such as Fe 2 O 3 、Fe 4 O 3 、Co 3 O 4 CuO, niO, etc. are receiving more and more attention because of their higher theoretical specific capacity and better safety performance. Wherein, fe 2 O 3 The theoretical specific capacity of the lithium ion battery cathode material is close to 3 times of that of the traditional carbon cathode material and can reach 1008mAh/g. Further, fe 2 O 3 The lithium ion battery cathode material also has the advantages of low cost, wide material source, safety, environmental protection and the like, and is a potential high-performance lithium ion battery cathode material. However, like other transition metal oxides, fe 2 O 3 The material has larger volume change in the charging and discharging process, the cycle performance is reduced, meanwhile, the voltage platform is higher due to the electronic conductivity difference, the porous iron oxide prepared by the measures of reducing the expansion of the iron oxide and improving the electronic conductivity improves the dynamic performance, the conductive agent is added to improve the expansion and improve the electronic conductivity, and the cycle performance is improved by optimizing the electrolyte. For example, chinese patent application No. CN201510150087.5 discloses a method for preparing an iron oxide microsphere negative electrode material for a lithium ion battery, and the iron oxide microsphere negative electrode material is prepared by a liquid phase method, but has the defects of low first efficiency, low power performance and the like.
Disclosure of Invention
The invention aims to overcome the defects and provide the iron oxide graphite composite material for the lithium ion battery, which can improve the power performance and the energy density of graphite and give consideration to the storage and the expansion performance of the material.
The invention also aims to provide a preparation method of the iron oxide graphite composite material for the lithium ion battery.
The iron oxide graphite composite material for the lithium ion battery is of a core-shell structure, the core is graphite, the shell is a complex composed of iron oxide/amorphous carbon/conductive agent, and the mass ratio of the shell is 1-30% by 100% of the mass of the composite negative electrode material;
the shell is composed of 10-60% of ferric oxide, 10-60% of amorphous carbon and 1-10% of conductive agent.
The invention relates to a preparation method of an iron oxide graphite composite material for a lithium ion battery, which comprises the following steps:
(1) According to the weight ratio of the inorganic iron compound: conductive agent: the mass ratio of the auxiliary agent is 100:1 to 5: 0.5-2, adding an inorganic iron compound into an organic solvent to prepare a solution with the concentration of 0.1-1 mol/L, uniformly dispersing, adding a conductive agent solution and an auxiliary agent, adding ammonia water to adjust the pH to 9-10, reacting at the temperature of 50-200 ℃ for 1-6 h, filtering, drying filter residues at the temperature of 80 ℃ for 24h, and sintering at the temperature of 200-500 ℃ to obtain porous iron oxide;
(2) According to the porous iron oxide: resin: the mass ratio of graphite is 10-20: 10 to 20:100, adding porous iron oxide into a resin solution with the concentration of 1-10 wt%, uniformly dispersing, adding graphite, transferring to a ball mill, dispersing for 1-24h at the rotating speed of 500-1000 RPM, drying for 24h at the temperature of 80 ℃, and carbonizing for 1-6 h at the temperature of 700-1000 ℃ in an inert atmosphere to obtain the iron oxide graphite composite material.
The preparation method of the iron oxide graphite composite material for the lithium ion battery comprises the following steps: the inorganic iron compound in the step (1) is one of ferric chloride, ferric nitrate or ferric sulfate.
The preparation method of the iron oxide graphite composite material for the lithium ion battery comprises the following steps: the conductive agent solution in the step (1) is graphene conductive solution, carbon nanotube conductive solution or carbon black conductive solution, the mass concentration is 1-5 wt%, and the solvent is N-methylpyrrolidone (NMP).
The preparation method of the iron oxide graphite composite material for the lithium ion battery comprises the following steps: the auxiliary agent in the step (1) is one of magnesium chloride or aluminum chloride.
The preparation method of the iron oxide graphite composite material for the lithium ion battery comprises the following steps: the organic solvent in the step (1) is one of N-methyl pyrrolidone, cyclohexane, carbon tetrachloride, xylene, toluene and butanediol.
The preparation method of the iron oxide graphite composite material for the lithium ion battery comprises the following steps: the resin in the step (1) is one of phenolic resin, furfural resin or epoxy resin, and one of methanol, ethanol, butanediol or butanol as a solvent.
Compared with the prior art, the invention has obvious beneficial effects, and the technical scheme can show that: according to the invention, an inorganic iron compound and an ammonia water alkaline solution are used to form an iron hydroxide suspension solution, and salt assistants such as magnesium chloride are added to destroy the colloid state of the iron hydroxide, so that the iron hydroxide is easy to precipitate, the precipitation effect of the iron hydroxide is improved, complete precipitation is promoted, and porous iron oxide is obtained; meanwhile, the porous iron oxide is coated on the surface of the graphite, so that the energy density is improved, and the power performance is improved due to the porous structure; meanwhile, the ferric oxide has a high voltage platform, and the safety performance is improved. Meanwhile, the electronic conductivity of the porous iron oxide is improved by adding the conductive agent.
Drawings
Fig. 1 is an SEM image of the iron oxide graphite composite material prepared in example 1.
Detailed Description
Example 1:
a preparation method of an iron oxide graphite composite material for a lithium ion battery comprises the following steps:
(1) Adding 100g of ferric chloride into 500ml of carbon tetrachloride, uniformly dispersing, adding 100ml of 3wt% graphene NMP conductive agent solution and 1g of magnesium chloride, adding ammonia water to adjust the pH to 9, reacting at 100 ℃ for 3 hours, filtering, drying filter residues at 80 ℃ for 24 hours, and sintering at 250 ℃ for 3 hours to obtain porous ferric oxide;
(2) Adding 15g of porous iron oxide into 300ml of ethanol solution of 5wt% phenolic resin, uniformly dispersing, adding 100g of artificial graphite, transferring to a ball mill, dispersing at the rotating speed of 800RPM for 12h, drying at 80 ℃ for 24h, and carbonizing at 800 ℃ for 3h under an argon inert atmosphere to obtain the iron oxide graphite composite material.
Example 2:
a preparation method of an iron oxide graphite composite material for a lithium ion battery comprises the following steps:
(1) Adding 100g of ferric nitrate into 500ml of N-methylpyrrolidone organic solvent, uniformly dispersing, adding 100ml of 1% NMP conductive agent solution of carbon nano tubes and 0.5g of aluminum chloride, adding ammonia water to adjust the pH to 10, reacting for 6 hours at the temperature of 50 ℃, filtering, drying filter residues for 24 hours at the temperature of 80 ℃, and sintering for 12 hours at the temperature of 200 ℃ to obtain porous ferric oxide;
(2) Adding 10g of porous iron oxide into a furfural resin methanol solution with the concentration of 100m and 10wt%, uniformly dispersing, adding 100g of artificial graphite, transferring to a ball mill, dispersing at the rotation speed of 500RPM for 24h, drying at the temperature of 80 ℃ for 24h, and carbonizing at the temperature of 700 ℃ for 6h under an argon inert atmosphere to obtain the iron oxide graphite composite material.
Example 3:
a preparation method of an iron oxide graphite composite material for a lithium ion battery comprises the following steps:
(1) Adding 100g of ferric sulfate into 500ml of cyclohexane organic solvent, uniformly dispersing, adding 100ml of NMP conductive agent solution containing 5wt% of carbon black and 2g of magnesium chloride, adding ammonia water to adjust the pH to 10, reacting at 200 ℃ for 1h, filtering, drying filter residue at 80 ℃ for 24h, and sintering at 500 ℃ for 1h to obtain porous ferric oxide;
(2) Adding 20g of porous iron oxide into 200ml of a 10wt% epoxy resin butanediol solution, uniformly dispersing, adding 1000g of artificial graphite, transferring to a ball mill, dispersing at the rotating speed of 1000RPM for 1h, vacuum drying at 80 ℃ for 24h, and carbonizing at 1000 ℃ for 1h under an argon inert atmosphere to obtain the iron oxide graphite composite material.
Comparative example 1:
a preparation method of an amorphous carbon-coated graphite composite material comprises the following steps:
100g of artificial graphite was added to 300ml of a 5wt% phenolic resin ethanol solution, and the mixture was transferred to a ball mill and dispersed at 800RPM for 12h, dried at 80 ℃ for 24h, and then carbonized at 800 ℃ for 3h under an inert atmosphere of argon gas at a temperature of 800 ℃ to obtain an amorphous carbon-coated graphite composite material.
Comparative example 2:
a preparation method of an iron oxide-graphite composite material comprises the following steps:
adding 15g of iron oxide into 300ml of 5wt% phenolic resin ethanol solution, uniformly dispersing, adding 100g of artificial graphite, transferring to a ball mill, dispersing at the rotating speed of 800RPM for 12h, drying at the temperature of 80 ℃ for 24h, and carbonizing at the temperature of 800 ℃ for 3h under an argon inert atmosphere to obtain the iron oxide-graphite composite material.
Experimental example:
(1) SEM test
The iron oxide-graphite composite anode material prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1. As can be seen from figure 1, the material has a core-shell structure, the particle size is between 10 and 15 mu m, and the particle size distribution is reasonable.
(2) Physical and chemical property test
The conductivity, tap density, specific surface area and particle size of the graphite composite negative electrode materials in examples 1-3 and comparative examples 1-2 were tested according to the test method in the standard GB/T-243339-2019 graphite-type negative electrode materials for lithium ion batteries. The test results are shown in table 1.
TABLE 1
| Negative electrode active material | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Conductivity (cm/S) | 5.4*10 -9 | 3.9*10 -9 | 1.2*10 -9 | 1.1*10 -10 | 1*10 -10 |
| Tap density (g/cm) 3 ) | 1.11 | 1.09 | 1.08 | 0.99 | 0.98 |
| Specific surface area (m) 2 /g) | 1.91 | 1.85 | 1.86 | 1.32 | 1.41 |
| Particle size (. Mu.m) | 13.2 | 13.4 | 13.7 | 14.1 | 14.8 |
As can be seen from table 1, the conductivity of the iron oxide graphite composite negative electrode materials prepared in examples 1 to 3 is significantly higher than that of comparative example 1, which may be caused by the electronic conductivity of the porous iron oxide lifting material with electronic conductivity on the surface of the example material, and the specific surface area is large.
(3) Button cell test
The iron oxide graphite composite negative electrode materials prepared in examples 1 to 3 and the graphite composite negative electrode material of the comparative example were assembled into button cells, respectively, as follows:
graphite composite negative electrode materials prepared in examples 1 to 3 and comparative examples 1 to 2The material is used as a negative electrode, and is assembled into a button cell together with a lithium sheet, an electrolyte and a diaphragm in a glove box with the content of argon and water lower than 0.1 ppm. Wherein the diaphragm is celegard 2400; the electrolyte is LiPF 6 In the electrolyte solution of (1), liPF 6 Is 1mol/L, and the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DMC) according to the weight ratio of 1:1 mixing the resulting mixed solution.
Marking the prepared button cell as A-1, B-1, C-1, D-1 and E-1, and testing the performance of the button cell by a blue tester under the following test conditions: charging and discharging at 0.1C rate, and cycling for 3 weeks at a voltage range of 0.05-2V. Simultaneously testing the specific capacity of the material at 2C and 0.1C, and calculating the rate capability at 2C/0.1C; the test results are shown in table 2.
TABLE 2
As can be seen from Table 2, the button cells prepared by using the iron oxide graphite composite negative electrode materials of examples 1-3 have significantly higher discharge capacities and efficiencies than those of comparative examples 1-2. Experimental results show that the graphite composite negative electrode material can enable a battery to have good discharge capacity and efficiency; because the porous iron oxide material has weaker reaction activity with the electrolyte, less lithium ions are consumed, and the first efficiency is improved; meanwhile, the electronic conductivity of the porous iron oxide is high, and the rate capability is improved.
(4) Laminate polymer battery performance test
The iron oxide graphite composite negative electrodes of examples 1 to 3 and comparative examples 1 to 2 were used as negative electrode active materials, and ternary materials (LiNi) were used as positive electrode active materials 1/3 Co 1/3 Mn 1/3 O 2 ) The electrolyte and the diaphragm are assembled into the 5Ah soft package battery.
Wherein the diaphragm is celegard 2400, and the electrolyte is LiPF 6 Solution (solvent is a mixed solution of EC and DEC in a volume ratio of 1, liPF 6 The concentration of (1.3 mol/L). The prepared soft package batteries are marked as A-2, B-2, C-2, D-2 and E-2 respectively.
In examples 1-3 and comparative examples 1-2, 5Ah soft-package batteries and corresponding negative electrode plates thereof were prepared, and the liquid absorption and retention capacity and cycle performance of the negative electrode plates thereof were tested, and the results are shown in tables 3-4. The test method is as follows:
1) Liquid absorption capacity:
and (3) adopting a 1mL burette, absorbing the electrolyte VML, dripping a drop on the surface of the pole piece, timing until the electrolyte is absorbed completely, recording the time t, and calculating the liquid absorption speed V/t of the pole piece. The test results are shown in table 3.
2) And (4) testing the liquid retention rate:
calculating the theoretical liquid absorption capacity m1 of the pole piece according to pole piece parameters, weighing the weight m2 of the pole piece, then placing the pole piece into electrolyte to soak for 24 hours, weighing the weight m3 of the pole piece, calculating the liquid absorption capacity m3-m2 of the pole piece, and calculating according to the following formula: liquid retention rate = (m 3-m 2) × 100%/m1.
3) Cycle performance: testing the cycle performance of the battery at the temperature of 25 +/-3 ℃ with the charge-discharge multiplying power of 1C/1C and the voltage range of 2.5V-4.2V;
4) And (3) rate performance test: and (4) carrying out 2C constant-current and constant-voltage charging on the soft package battery, and calculating the ratio of the charging capacity under the constant voltage to the charging capacity of the constant voltage and the constant current.
TABLE 3
As can be seen from Table 3, the liquid absorbing and retaining capacities of the iron oxide graphite composite materials obtained in examples 1 to 3 are significantly higher than those of the comparative examples, i.e., the iron oxide graphite composite material of the present invention has a high specific surface area and a porous structure thereof, and the liquid absorbing capacity of the material is improved.
TABLE 4
The cycle performance retention rate and the constant current ratio of the soft package battery prepared from the negative electrode material obtained in table 4 can be seen from the table, the cycle performance of the battery in the embodiment is obviously better than that of the battery in the comparative example, because the iron oxide graphite composite material obtained in the embodiment has high liquid absorption and retention capacity of the specific surface area improving material, and further improves the cycle performance; meanwhile, the iron oxide graphite composite material in the embodiment has high electronic conductivity, so that the charging capacity of the material is improved, namely the constant current ratio of the soft package battery prepared in the embodiment is improved.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, they are not intended to limit the scope of the present invention. Various modifications and changes may be made by those skilled in the art, and any modifications, equivalents, and improvements made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. An iron oxide graphite composite material for a lithium ion battery is characterized in that: the composite material is in a core-shell structure, the inner core is graphite, the shell is a complex composed of ferric oxide/amorphous carbon/conductive agent, and the mass ratio of the shell is 1-30% by 100% of the mass of the composite negative electrode material.
2. The iron oxide graphite composite material for lithium ion batteries according to claim 1, wherein: the shell is composed of 10-60% of ferric oxide, 10-60% of amorphous carbon and 1-10% of conductive agent.
3. A preparation method of an iron oxide graphite composite material for a lithium ion battery comprises the following steps:
(1) According to the weight ratio of the inorganic iron compound: conductive agent: the mass ratio of the auxiliary agent is 100:1 to 5: 0.5-2, adding an inorganic iron compound into an organic solvent to prepare a mixture with the concentration of 0.1-1 mol/L, uniformly dispersing, adding a conductive agent solution and an auxiliary agent, adding ammonia water to adjust the pH to 9-10, reacting at the temperature of 50-200 ℃ for 1-6 h, filtering, drying filter residues at the temperature of 80 ℃ for 24h, and sintering at the temperature of 200-500 ℃ to obtain porous iron oxide;
(2) According to the porous iron oxide: resin: the mass ratio of the graphite is 10-20: 10 to 20:100, adding porous iron oxide into a resin solution with the concentration of 1-10 wt%, uniformly dispersing, adding graphite, transferring to a ball mill, dispersing for 1-24h at the rotating speed of 500-1000 RPM, drying for 24h at the temperature of 80 ℃, and carbonizing for 1-6 h at the temperature of 700-1000 ℃ in an inert atmosphere to obtain the iron oxide graphite composite material.
4. The method of claim 3, wherein: the inorganic iron compound in the step (1) is one of ferric chloride, ferric nitrate or ferric sulfate.
5. The method of claim 3, wherein: the conductive agent solution in the step (1) is graphene conductive solution, carbon nanotube conductive solution or carbon black conductive solution, the mass concentration is 1-5 wt%, and the solvent is N-methylpyrrolidone.
6. The method of claim 3, wherein: the auxiliary agent in the step (1) is one of magnesium chloride or aluminum chloride.
7. The method of claim 3, wherein: the organic solvent in the step (1) is one of N-methyl pyrrolidone, cyclohexane, carbon tetrachloride, xylene, toluene and butanediol.
8. The method of claim 3, wherein: the resin in the step (1) is one of phenolic resin, furfural resin or epoxy resin, and one of methanol, ethanol, butanediol or butanol as a solvent.
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