CN108899489A - A kind of preparation method of carbon coating lithium iron oxide cell negative electrode material - Google Patents
A kind of preparation method of carbon coating lithium iron oxide cell negative electrode material Download PDFInfo
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- CN108899489A CN108899489A CN201810630170.6A CN201810630170A CN108899489A CN 108899489 A CN108899489 A CN 108899489A CN 201810630170 A CN201810630170 A CN 201810630170A CN 108899489 A CN108899489 A CN 108899489A
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- iron oxide
- humic acid
- negative electrode
- electrode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods of carbon coating lithium iron oxide cell negative electrode material, and the method is using nano iron oxide as major ingredient, and raw material sources are extensive, cheap and easy to get, and preparation process is simply easy；Humic acid is used for negative electrode material carbon coating agent by the present invention, and negative electrode material specific capacity is high, and cycle performance and high rate performance are excellent.
Description
Technical field
The present invention relates to battery material fields, and in particular to a kind of preparation side of carbon coating lithium iron oxide cell negative electrode material
Method.
Background technique
The rapid development of modern industry, the mankind increasingly increase the demand of the energy.The world the utilized energy at present
85% from fossil feedstock (coal, petroleum, natural gas etc.), these raw materials be it is non-renewable, caused by environmental pollution
Constantly aggravating.Therefore, the development of green energy resource and its material, for realizing the 21st century strategy of sustainable development,
Alleviating energy crisis and mitigation pollution pressure all have very important significance.
It by lithium metal or lithium alloy is negative electrode material, using the battery of non-aqueous electrolytic solution that lithium battery, which is a kind of,.Due to
The chemical characteristic of lithium metal is very active, so that the processing of lithium metal, preservation, use, very high to environmental requirement, so, lithium
Battery is not applied for a long time, and with the development of technology, present lithium battery has become mainstream.Lithium battery can substantially divide
For two classes：Lithium metal battery and lithium ion battery.Lithium ion battery does not contain the lithium of metallic state, and can charge.Lithium
It is positive electrode that ion battery, which is usually using lithium alloy metals oxide, graphite is negative electrode material.
However, the embedding lithium maximum capacity of theory of graphite is only 372mAh/g, and irreversible loss is big for the first time, multiplying power discharging
Can be poor, in addition, the partial solvent of electrolyte can also follow insertion, be easy to happen the variation of structure in lithium ion insertion.Obviously
It is not able to satisfy that vehicle lithium ion battery is high-power, requirement of high capacity.Therefore, in field of lithium, it is badly in need of negative electrode material at present
Update.
Transition metal oxide (di-iron trioxide) has the advantages such as theoretical specific capacity height, rich content, pollution-free, can make
For the negative electrode material of lithium secondary battery.However, there is also one while di-iron trioxide highlights advantage as lithium cell negative pole material
A little disadvantages：First is that body phase ferricoxide poorly conductive, is unfavorable for the transmission of electronics；Second is that in charge and discharge process, three oxygen of body phase
Change the easy dusting of two iron to reunite, cycle performance of battery is caused sharply to decline.
Summary of the invention
The present invention provides a kind of preparation method of carbon coating lithium iron oxide cell negative electrode material, and the method uses nano oxygen
Change iron as major ingredient, raw material sources are extensive, cheap and easy to get, and preparation process is simply easy；Humic acid is used for negative electrode material by the present invention
Carbon coating agent, negative electrode material specific capacity is high, and cycle performance and high rate performance are excellent.
To achieve the goals above, the present invention provides a kind of preparation method of carbon coating lithium iron oxide cell negative electrode material,
This method comprises the following steps：
（1）Prepare nano iron oxide
Ferric trichloride and potassium dihydrogen phosphate or ortho phosphorous acid potassium are added in the mixed liquor of water and ethylene glycol, reaction solution is obtained；?
The concentration of ferric trichloride is 0.02-0.025mol/L in the reaction solution, and the concentration of potassium dihydrogen phosphate or ortho phosphorous acid potassium is
0.15-0.35mmol/L；In the mixed liquor of water and ethylene glycol, the percentage by volume of ethylene glycol is 15-45%；
The reaction solution is added in reaction kettle, 95-100 DEG C of hydro-thermal reaction 50-120h, after being then so cooled to room temperature, centrifugation,
Washing, i.e. acquisition nanometer di-iron trioxide；
（2）Commercial solid humic acid is added to the potassium hydroxide solution of 1-1.5mol/L, the matter of humic acid and potassium hydroxide solution
Amount is than being 1：（3-5）, 60-65 DEG C of stirring 20-40min, centrifuge separation, take supernatant and be adjusted to pH=2-3, stand 12-14h, sink
Humic acid of the starch after drying is to get purification；
（3）Humic acid after purification is added in the potassium hydroxide solution of 1-1.5mol/L, heating, stirring are completely molten to solid
Solution；Above-mentioned nano iron oxide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery；Exist again
950-1000 DEG C, calcine 2-4h in argon atmosphere, it is centrifugation, washing, dry to get carbon coating lithium iron oxide cell negative electrode material.
Preferably, concentration of the humic acid after purification in potassium hydroxide solution is 14-15g/L, the humic acid after purification
Mass ratio with the nano iron oxide is（6-7）：（3.5-4）.
The invention has the advantages that and remarkable result：
（1）Using nano iron oxide as major ingredient, raw material sources are extensive, cheap and easy to get, and preparation process is simply easy；
（2）Humic acid is used for negative electrode material carbon coating agent by the present invention, and negative electrode material specific capacity is high, cycle performance and high rate performance
It is excellent.
Specific embodiment
Embodiment one
Ferric trichloride and potassium dihydrogen phosphate are added in the mixed liquor of water and ethylene glycol, reaction solution is obtained；In the reaction solution
The concentration of ferric trichloride is 0.02mol/L, and the concentration of potassium dihydrogen phosphate or ortho phosphorous acid potassium is 0.15mmol/L；Water and ethylene glycol
Mixed liquor in, the percentage by volume of ethylene glycol is 15%.
The reaction solution is added in reaction kettle, 95 DEG C of hydro-thermal reaction 50h after being then so cooled to room temperature, are centrifuged, wash
It washs, i.e. acquisition nanometer di-iron trioxide.
Commercial solid humic acid is added to the potassium hydroxide solution of 1mol/L, the mass ratio of humic acid and potassium hydroxide solution
It is 1：3,60 DEG C of stirring 20min, centrifuge separation, take supernatant and are adjusted to pH=2, stand 12h, sediment is through dry to get purification
Humic acid afterwards.
Humic acid after purification is added in the potassium hydroxide solution of 1mol/L, heating, stirring to solid are completely dissolved；Again
Above-mentioned nano iron oxide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery；Again 950
DEG C, calcine 2h in argon atmosphere, it is centrifugation, washing, dry to get carbon coating lithium iron oxide cell negative electrode material.Wherein, after purification
Concentration of the humic acid in potassium hydroxide solution be 14g/L, the mass ratio of humic acid and the nano iron oxide after purification
It is 6：3.5.
Embodiment two
Ferric trichloride and ortho phosphorous acid potassium are added in the mixed liquor of water and ethylene glycol, reaction solution is obtained；In the reaction solution
The concentration of ferric trichloride is 0.025mol/L, and the concentration of potassium dihydrogen phosphate or ortho phosphorous acid potassium is 0.35mmol/L；Water and second two
In the mixed liquor of alcohol, the percentage by volume of ethylene glycol is 45%.
The reaction solution is added in reaction kettle, 100 DEG C of hydro-thermal reaction 120h after being then so cooled to room temperature, are centrifuged, wash
It washs, i.e. acquisition nanometer di-iron trioxide.
Commercial solid humic acid is added to the potassium hydroxide solution of 1.5mol/L, the quality of humic acid and potassium hydroxide solution
Than being 1：5,65 DEG C of stirring 40min, centrifuge separation, take supernatant and are adjusted to pH=3, stand 14h, sediment is through dry to get essence
Humic acid after system.
Humic acid after purification is added in the potassium hydroxide solution of 1.5mol/L, heating, stirring to solid are completely dissolved；
Above-mentioned nano iron oxide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery；Exist again
1000 DEG C, calcine 4h in argon atmosphere, it is centrifugation, washing, dry to get carbon coating lithium iron oxide cell negative electrode material.Wherein, smart
Concentration of the humic acid in potassium hydroxide solution after system is 15g/L, the matter of humic acid and the nano iron oxide after purification
Amount is than being 7：4.
Using above-described embodiment one, two products therefrom materials as being used for cathode of lithium battery, with just extremely LiFePO 4 material
The test battery pack of composition carries out cyclical stability test, and discharge capacity is respectively 1513mAh/g and 1544mAh/g for the first time, is followed
Capacity is 1322mAh/g and 1370mAh/g after ring 200 times, has good cyclical stability.
Claims (2)
1. a kind of preparation method of carbon coating lithium iron oxide cell negative electrode material, this method comprises the following steps：
（1）Prepare nano iron oxide
Ferric trichloride and potassium dihydrogen phosphate or ortho phosphorous acid potassium are added in the mixed liquor of water and ethylene glycol, reaction solution is obtained；?
The concentration of ferric trichloride is 0.02-0.025mol/L in the reaction solution, and the concentration of potassium dihydrogen phosphate or ortho phosphorous acid potassium is
0.15-0.35mmol/L；In the mixed liquor of water and ethylene glycol, the percentage by volume of ethylene glycol is 15-45%；
The reaction solution is added in reaction kettle, 95-100 DEG C of hydro-thermal reaction 50-120h, after being then so cooled to room temperature, centrifugation,
Washing, i.e. acquisition nanometer di-iron trioxide；
（2）Commercial solid humic acid is added to the potassium hydroxide solution of 1-1.5mol/L, the matter of humic acid and potassium hydroxide solution
Amount is than being 1：（3-5）, 60-65 DEG C of stirring 20-40min, centrifuge separation, take supernatant and be adjusted to pH=2-3, stand 12-14h, sink
Humic acid of the starch after drying is to get purification；
（3）Humic acid after purification is added in the potassium hydroxide solution of 1-1.5mol/L, heating, stirring are completely molten to solid
Solution；Above-mentioned nano iron oxide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery；Exist again
950-1000 DEG C, calcine 2-4h in argon atmosphere, it is centrifugation, washing, dry to get carbon coating lithium iron oxide cell negative electrode material.
2. method according to claim 1 or 2, which is characterized in that the humic acid after purification is dense in potassium hydroxide solution
Degree is 14-15g/L, and the mass ratio of humic acid and the nano tin dioxide after purification is（6-7）：（3.5-4）.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111193026A (en) * | 2020-01-08 | 2020-05-22 | 河南城建学院 | Preparation method of fusiform iron oxide single crystal nano material |
| CN111244440A (en) * | 2020-01-20 | 2020-06-05 | 宁波瞬能科技有限公司 | In-situ carbon-coated Fe3O4Composite material, preparation method thereof and application thereof in lithium ion battery |
| CN111517297A (en) * | 2020-04-02 | 2020-08-11 | 太原理工大学 | Preparation method and application of heterostructure/graphene composite material |
| CN112331824A (en) * | 2020-10-14 | 2021-02-05 | 华南师范大学 | Nitrogen-doped carbon-coated nano ferroferric oxide composite material and preparation method thereof |
| CN112421044A (en) * | 2020-11-20 | 2021-02-26 | 北京理工大学重庆创新中心 | Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816595A (en) * | 2017-03-09 | 2017-06-09 | 合肥工业大学 | A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon |
| CN106935823A (en) * | 2017-03-20 | 2017-07-07 | 郑州大学 | A kind of lithium ion battery negative material Sn/C and preparation method thereof |
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2018
- 2018-06-19 CN CN201810630170.6A patent/CN108899489A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816595A (en) * | 2017-03-09 | 2017-06-09 | 合肥工业大学 | A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon |
| CN106935823A (en) * | 2017-03-20 | 2017-07-07 | 郑州大学 | A kind of lithium ion battery negative material Sn/C and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111193026A (en) * | 2020-01-08 | 2020-05-22 | 河南城建学院 | Preparation method of fusiform iron oxide single crystal nano material |
| CN111244440A (en) * | 2020-01-20 | 2020-06-05 | 宁波瞬能科技有限公司 | In-situ carbon-coated Fe3O4Composite material, preparation method thereof and application thereof in lithium ion battery |
| CN111244440B (en) * | 2020-01-20 | 2021-06-08 | 宁波瞬能科技有限公司 | In-situ carbon-coated Fe3O4Composite material, preparation method thereof and application thereof in lithium ion battery |
| CN111517297A (en) * | 2020-04-02 | 2020-08-11 | 太原理工大学 | Preparation method and application of heterostructure/graphene composite material |
| CN111517297B (en) * | 2020-04-02 | 2023-03-24 | 太原理工大学 | Preparation method and application of heterostructure/graphene composite material |
| CN112331824A (en) * | 2020-10-14 | 2021-02-05 | 华南师范大学 | Nitrogen-doped carbon-coated nano ferroferric oxide composite material and preparation method thereof |
| CN112331824B (en) * | 2020-10-14 | 2022-01-18 | 华南师范大学 | Nitrogen-doped carbon-coated nano ferroferric oxide composite material and preparation method thereof |
| CN112421044A (en) * | 2020-11-20 | 2021-02-26 | 北京理工大学重庆创新中心 | Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur battery |
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Application publication date: 20181127 |