CN112777591B - Preparation method of lithium battery negative electrode material - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 65
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004471 Glycine Substances 0.000 claims abstract description 22
- 239000010931 gold Substances 0.000 claims abstract description 21
- 229910052737 gold Inorganic materials 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000009835 boiling Methods 0.000 claims abstract description 18
- 239000010406 cathode material Substances 0.000 claims abstract description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000001509 sodium citrate Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000010355 oscillation Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 gold ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012073 inactive phase Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
- C01B32/196—Purification
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C01B2204/00—Structure or properties of graphene
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- C01B2204/22—Electronic properties
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Abstract
The invention provides a preparation method of a lithium battery negative electrode material. The preparation steps are as follows: adding graphene oxide into a nitric acid solution for ultrasonic oscillation; heating, boiling, refluxing, taking out, washing and filtering to obtain acid graphene oxide; adding the sodium citrate solution into the chloroauric acid solution, and heating and boiling to obtain gold sol; taking acid graphene oxide, and adding water to obtain an acid graphene oxide dispersion liquid; dripping the solution into a gold sol solution, and vibrating and depositing to obtain gold-doped graphene oxide; dissolving silica sol and glycine in deionized water to obtain a silicon dioxide/glycine solution; adding gold-doped graphene oxide, and performing ultrasonic treatment; transferring the mixture into a high-pressure kettle for treatment; cooling to room temperature, washing and drying; taking out and putting into a tubular furnace, and calcining under the protection of nitrogen; and naturally cooling to obtain the lithium battery cathode material. The lithium battery cathode material prepared by the invention has the advantages that the specific structure and the hybrid structure supported by the conductive carbon obviously improve the conductivity of SiO, so that the electrochemical performance is improved.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method of a lithium battery cathode material.
Background
With the development of science and technology and the increasing pollution caused by traditional petroleum energy, the demand of people for novel renewable energy is urgent day by day. The lithium ion battery is an ideal renewable energy source due to the advantages of high energy density, long cycle life, environmental friendliness and the like. The electrode material is one of the key factors determining the performance of the lithium ion battery, the current commercialized carbon negative electrode material is close to the theoretical capacity (372mAh/g) and is difficult to have a space for improvement, and compared with the carbon negative electrode material, the theoretical specific capacity of silicon is up to 4200mAh/g, so that the carbon negative electrode material becomes a hot point of research. However, in the process of lithium intercalation and deintercalation, the volume expansion effect of silicon is as high as 300%, so that the first efficiency and the cycle stability are relatively poor, and the pulverization failure of the electrode material is easily caused. SiO as a lithium ion battery cathode material has excellent electrochemical performance, and can form an inactive phase Li in the process of lithium intercalation for the first time2O and Li4SiO4. Although the first irreversible capacity loss is increased, the first irreversible capacity loss is increasedThe effect of relieving the volume expansion is achieved, but the effect is still poor. Therefore, it is important to research and develop a more effective negative electrode material.
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to provide a preparation method of a lithium battery cathode material, and the prepared lithium battery cathode material obviously improves the conductivity of SiO due to the unique structure and the hybrid structure supported by conductive carbon, thereby improving the electrochemical performance.
The technical scheme is as follows: a preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 125-130 ℃, refluxing for 10-20h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(4) taking 75mg of acid graphene oxide, and adding 100-300mL of water to obtain an acid graphene oxide dispersion liquid;
(5) dripping into gold sol solution, and vibrating and depositing for 7-8min to obtain gold-doped graphene oxide;
(6) dissolving 1.5-5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(7) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3h at the temperature of 700 and 800W;
(8) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(9) naturally cooling to room temperature, sequentially washing with distilled water and ethanol for 3-5 times, and oven drying at 60 deg.C;
(10) taking out and putting into a tubular furnace, heating to 700 and 750 ℃ at the speed of 5 ℃/min under the protection of nitrogen, and calcining for 2 h;
(11) and naturally cooling to obtain the lithium battery cathode material.
Further, the mass of the silica sol in the step (5) is 4 g.
Further, the ultrasonic power in the step (7) is 850W.
Further, the calcination temperature in the step (10) is 730 ℃.
Has the advantages that:
1. the nitric acid reflux oxidation is adopted, so that not only can the graphene oxide be purified and impurities be removed, but also oxygen-containing functional groups can be introduced to the surface of the graphene oxide, the hydrophilicity of the graphene oxide is improved, and the graphene oxide can have greater application potential.
2. The nitric acid oxidation constructs defect sites, some hydrophilic groups such as oxygen-containing functional groups and the like on the surface of the graphene oxide, and gold ions can form stable coordination compounds with various ligands and exist in an ionic form in a solution, so that the deposition doping of the gold ions on the graphene oxide in the solution is realized.
3. According to the invention, the hybrid of the silica sol, the glycine and the gold-doped graphene oxide is successfully prepared through self-assembly of the silica sol, the glycine and the gold-doped graphene oxide in continuous ultrasonic, hydrothermal and thermal treatment, wherein the gold-doped graphene oxide can effectively improve the cycle performance of the carbon-coated silicon dioxide composite material as a LiBs cathode material, and the structural stability of the carbon-coated silicon dioxide composite material is improved. Meanwhile, the unique structure and the hybrid structure supported by conductive carbon obviously improve the conductivity of SiO, thereby improving the electrochemical performance.
Detailed Description
Example 1
A preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 125 ℃, refluxing for 10h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(4) taking 75mg of acid graphene oxide, and adding 100mL of water to obtain an acid graphene oxide dispersion liquid;
(5) dripping into gold sol solution, and vibrating and depositing for 7min to obtain gold-doped graphene oxide;
(6) dissolving 1.5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(7) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3 hours at 700W;
(8) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(9) naturally cooling to room temperature, washing with distilled water and ethanol for 3 times, and oven drying at 60 deg.C;
(10) taking out, putting into a tubular furnace, heating to 700 ℃ at a speed of 5 ℃/min under the protection of nitrogen, and calcining for 2 h;
(11) and naturally cooling to obtain the lithium battery cathode material.
Example 2
A preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 126 ℃, refluxing for 12h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(4) taking 75mg of acid graphene oxide, and adding 150mL of water to obtain an acid graphene oxide dispersion liquid;
(5) dripping into gold sol solution, and vibrating and depositing for 7.5min to obtain gold-doped graphene oxide;
(6) dissolving 2.5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(7) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3 hours at 720W;
(8) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(9) naturally cooling to room temperature, washing with distilled water and ethanol for 4 times, and oven drying at 60 deg.C;
(10) taking out, putting into a tubular furnace, heating to 720 ℃ at a speed of 5 ℃/min under the protection of nitrogen, and calcining for 2 h;
(11) and naturally cooling to obtain the lithium battery cathode material.
Example 3
A preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 127 ℃, refluxing for 15h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(4) taking 75mg of acid graphene oxide, and adding 200mL of water to obtain an acid graphene oxide dispersion liquid;
(5) dripping into gold sol solution, and vibrating and depositing for 7.5min to obtain gold-doped graphene oxide;
(6) dissolving 3.5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(7) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3 hours at 750W;
(8) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(9) naturally cooling to room temperature, washing with distilled water and ethanol for 4 times, and oven drying at 60 deg.C;
(10) taking out, putting into a tubular furnace, heating to 730 ℃ at the speed of 5 ℃/min under the protection of nitrogen, and calcining for 2 h;
(11) and naturally cooling to obtain the lithium battery cathode material.
Example 4
A preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 128 ℃, refluxing for 18h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(4) taking 75mg of acid graphene oxide, and adding 250mL of water to obtain an acid graphene oxide dispersion liquid;
(5) dripping into gold sol solution, and vibrating and depositing for 7.5min to obtain gold-doped graphene oxide;
(6) dissolving 4g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(7) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3 hours at 780W;
(8) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(9) naturally cooling to room temperature, washing with distilled water and ethanol for 4 times, and oven drying at 60 deg.C;
(10) taking out and putting into a tubular furnace, heating to 740 ℃ at the speed of 5 ℃/min under the protection of nitrogen, and calcining for 2 h;
(11) and naturally cooling to obtain the lithium battery cathode material.
Example 5
A preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 130 ℃, refluxing for 20h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(4) taking 75mg of acid graphene oxide, and adding 300mL of water to obtain an acid graphene oxide dispersion liquid;
(5) dripping into gold sol solution, and vibrating and depositing for 8min to obtain gold-doped graphene oxide;
(6) dissolving 5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(7) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3 hours at 800W;
(8) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(9) naturally cooling to room temperature, washing with distilled water and ethanol for 5 times, and oven drying at 60 deg.C;
(10) taking out and putting into a tubular furnace, heating to 750 ℃ under the protection of nitrogen, and calcining for 2 h;
(11) and naturally cooling to obtain the lithium battery cathode material.
Comparative example 1
This comparative example differs from example 5 in that the acid oxidation treatment was not performed, as follows:
a preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(2) taking 75mg of graphene oxide, and adding 300mL of water to obtain a graphene oxide dispersion solution;
(3) dripping into gold sol solution, and vibrating and depositing for 8min to obtain gold-doped graphene oxide;
(4) dissolving 5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(5) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3 hours at 800W;
(6) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(7) naturally cooling to room temperature, washing with distilled water and ethanol for 5 times, and oven drying at 60 deg.C;
(8) taking out and putting into a tubular furnace, heating to 750 ℃ under the protection of nitrogen, and calcining for 2 h;
(9) and naturally cooling to obtain the lithium battery cathode material.
Comparative example 2
The difference between the comparative example and the example 5 is that the graphene is not doped with gold, and the specific difference is as follows:
a preparation method of a lithium battery negative electrode material comprises the following steps:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 130 ℃, refluxing for 20h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) dissolving 5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(4) adding acid graphene oxide, and performing ultrasonic treatment for 3 hours at 800W;
(5) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(6) naturally cooling to room temperature, washing with distilled water and ethanol for 5 times, and oven drying at 60 deg.C;
(7) taking out and putting into a tubular furnace, heating to 750 ℃ under the protection of nitrogen, and calcining for 2 h;
(8) and naturally cooling to obtain the lithium battery cathode material.
Assembling the battery:
the lithium battery negative electrode material, the conductive agent carbon black and the adhesive acrylic resin are mixed into slurry according to the mass ratio of 6:2:2, the slurry is coated on a Cu foil, then the Cu foil is dried in vacuum for 2 hours at 150 ℃, a copper foil is punched into an electrode plate with a certain diameter by a punching machine after a solvent is removed, the electrode plate is placed in a tablet machine and is set to be 6MPa, and the electrode plate is pressed for more than 5 seconds. Other gas content requirement H in argon filled glove box2Volume fraction of O less than 5X 10-7. And O2Is less than 5 x 10-7Assembling the battery by using a CR2016 button battery as a test model, wherein the negative electrode material adopts the negative electrode material of the lithium battery, the positive electrode adopts a metal lithium sheet, and the electrolyte is 1mol/L LiPF6And ethylene carbonate/dimethyl carbonate (volume ratio 1:1), and Celgard 2400 polypropylene porous membrane was used as a separator.
And (3) testing the electrochemical performance of the battery:
and at normal temperature, a Land battery test system is adopted to perform constant current charge-discharge cycle performance test and multiple rate cycle performance test at a certain current density within 0.01-3V. The specific capacity was measured at a current density of 186mA · h/g.
TABLE 1
| Coulomb efficiency/% | Specific capacity mA.h/g | |
| Example 1 | 99.2 | 901.7 |
| Example 2 | 99.4 | 906.4 |
| Example 3 | 99.5 | 912.4 |
| Example 4 | 99.7 | 921.8 |
| Example 5 | 99.5 | 920.1 |
| Comparative example 1 | 94.5 | 834.6 |
| Comparative example 2 | 95.0 | 801.2 |
Claims (4)
1. The preparation method of the lithium battery negative electrode material is characterized by comprising the following steps of:
(1) adding 75mg of graphene oxide into 100ml of prepared nitric acid solution with the mass fraction of 40%, and ultrasonically oscillating for 20 min;
(2) heating and boiling to 125-130 ℃, refluxing for 10-20h, taking out, washing to be neutral, and filtering to obtain acid graphene oxide;
(3) adding 15ml of sodium citrate solution into 100ml of chloroauric acid solution, heating and boiling for 30min to obtain gold sol solution;
(4) taking 75mg of acid graphene oxide, and adding 100-300mL of water to obtain an acid graphene oxide dispersion liquid;
(5) dripping into gold sol solution, and vibrating and depositing for 7-8min to obtain gold-doped graphene oxide;
(6) dissolving 1.5-5g of silica sol and 5g of glycine in deionized water to obtain a silicon dioxide/glycine solution;
(7) adding gold-doped graphene oxide, and performing ultrasonic treatment for 3h at the temperature of 700 and 800W;
(8) transferring to an autoclave, and keeping the temperature at 190 ℃ for 12 h;
(9) naturally cooling to room temperature, sequentially washing with distilled water and ethanol for 3-5 times, and oven drying at 60 deg.C;
(10) taking out and putting into a tubular furnace, heating to 700 and 750 ℃ at the speed of 5 ℃/min under the protection of nitrogen, and calcining for 2 h;
(11) and naturally cooling to obtain the lithium battery cathode material.
2. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein the mass of the silica sol in the step (6) is 4 g.
3. The method for preparing a negative electrode material for a lithium battery according to claim 1, wherein: the ultrasonic power in the step (7) is 850W.
4. The method as claimed in claim 1, wherein the calcination temperature in the step (10) is 730 ℃.
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| KR101271249B1 (en) * | 2010-12-22 | 2013-06-10 | 한국과학기술원 | N-doped Transparent Graphene Film and Method for Preparing the Same |
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