CN107195879A - A kind of preparation method of the graphite oxide negative material of high performance lithium ion battery - Google Patents
A kind of preparation method of the graphite oxide negative material of high performance lithium ion battery Download PDFInfo
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- CN107195879A CN107195879A CN201710319657.8A CN201710319657A CN107195879A CN 107195879 A CN107195879 A CN 107195879A CN 201710319657 A CN201710319657 A CN 201710319657A CN 107195879 A CN107195879 A CN 107195879A
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- Prior art keywords
- lithium ion
- ion battery
- negative material
- graphite oxide
- high performance
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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
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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
- H01M4/58—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
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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 provides a kind of preparation method of the graphite oxide negative material of high performance lithium ion battery, natural graphite powder is aoxidized with strong acid and oxidant, then carrying out low temperature hair in zero degree should, middle temperature reaction in a water bath, adds deionized water high-temperature process, is cooled to after room temperature and adds a certain amount of hydrogen peroxide again, warm water stirring suction filtration is added after the completion of question response, cleaned repeatedly, dried in drying box with watery hydrochloric acid again, graphite oxide negative material is made.The electrode obtained material compares the graphite cathode of conventional lithium ion battery, very high performance is shown, in 1.875Ag‑1Discharge current under capacity still have 261.4mAhg‑1, far above the 43.7mAhg of graphite powder‑1.The preparation technology is simple, controllable, and cost is relatively low, and security is higher, can effectively meet development and the demand of existing lithium ion battery.
Description
Technical field
The present invention relates to a kind of nano material preparation technology, belong to the technology of high performance lithium ionic cell cathode material manufacture
Field.
Background technology
In the today's society of sustainable development, energy problem and environmental problem become increasingly conspicuous.And use clean energy resource electronic
Automobile replaces the fuel power automobile of original high pollution imperative.Lithium ion battery is because energy density is high, environment phase
Capacitive is good, safe and reliable, memory-less effect, stable work in work the advantages of, it has also become one of candidate of electrical source of power of new generation.
In recent years, with the development of science and technology to performance requirements such as lithium ion battery energy density per unit volume and charging intervals not
Disconnected to improve, electric bicycle and electric automobile propose higher requirement to course continuation mileage, cycle life of lithium ion battery etc..
Electrode material is as the core and key technology of lithium ion battery, and battery performance requirements direct correlation is each positive and negative electrode material
In item performance indications, and performance of the negative material to performance of lithium ion battery has bigger influence；The negative pole of lithium ion battery
Material has carbon material, intermetallic compound etc., at present, industrialized lithium ion battery negative material be mainly carbon material (graphite,
Hard carbon, soft carbon etc.) and lithium titanate, graphite-like carbon material among these, with relatively low lithium insertion/deintercalation current potential, suitable reversible
Capacity and aboundresources, it is cheap the advantages of, while technology is most ripe, most widely used；Although graphite material is widely used,
But irreversible capacity loss is very high first without the natural graphite negative electrode material by modification, capacity declines during high power charging-discharging
Comparatively fast, the selectivity to electrolyte is higher, and high rate during charging-discharging is bad, and the lithium ion of solvation can be inserted in cyclic process
Enter to graphite layers, its theoretical specific capacity only has 372mAh/g, thus limit the further raising of lithium ion battery specific energy,
The demand of growing high-energy Portable power source can not be met.
For this problem, research at present is main to be improved using methods such as surface treatment, Surface coating and element dopings
Its electrical conductivity.Wherein, the graphene most study obtained by redox processing is carried out to graphite, graphene has excellent fax
The property led, higher specific surface area (2600m2/ g), excellent thermal property and mechanical performance, it is considered to be preferable lithium battery
Pole material, has huge application space as lithium ion battery negative material.Simple graphene theoretical specific capacity is
744mAh/g, although better than graphite, but it is not so good as original graphite on cyclical stability, be not suitable for directly as lithium ion battery
Negative material.It is generally necessary to carry out complicated modification, doping to graphene again or be combined with other materials.
At present, although surface is modified, Surface coating improves the surface texture and chemistry of native graphite to a certain extent
Performance, reduces corrosion of the electrolyte to graphite flake layer, is effectively improved negative material first charge-discharge efficiency, but to graphite cathode
The improvement of the raising of material property, particularly high rate during charging-discharging is not very particularly significant, so that graphite cathode material exists
The application of high-end lithium ion battery is by a definite limitation, it is impossible to meet the requirement of current fast charging and discharging performance.
The content of the invention
Technical problem：In order to overcome the above-mentioned deficiencies of the prior art, directly made by studying the graphite of different degree of oxidations
Simple there is provided a kind of technique is gone out for negative material, cost is low, it is easy to industrialized production and excellent, the stable material of electrochemical properties
Prepared by material, be specifically to provide a kind of preparation method of the graphite oxide negative material of high performance lithium ion battery.
Technical scheme：A kind of preparation method of the graphite oxide negative material of high performance lithium ion battery of the present invention includes
Following steps：
Step 1) graphite powder and strong acid dispensing are subjected to low-temp reaction, oxidant is then slowly added to while stirring, low
Temperature reaction a period of time；
Step 2) by step 1) reactant carry out middle temperature and react, deionized water progress pyroreaction is added afterwards；
Step 3) step 2) reaction product be cooled to after room temperature, add hydrogen peroxide, add warm water after the completion of question response
Suction filtration, and rear vacuum drying is washed repeatedly with watery hydrochloric acid, produce graphite oxide negative material.
Wherein：
In step 1) in, the strong acid is the concentrated sulfuric acid, and oxidant is potassium permanganate.
Step 1) in, the mass ratio of the strong acid and oxidant and graphite is：23x:3.5x:1, wherein 0.5<x<4.
Step 1) in, low-temp reaction whipping temp is 0-10 DEG C, and 2-30 minute sulfuric acid reaction time, after addition oxidant
Reaction time is 0.5-6 hours.
Step 2) in, middle temperature reaction temperature is 20-50 degree, and the reaction time is 0.5-6 hours.
Pyroreaction temperature is 70-98 DEG C, and the time is 0.5-5 hours.
Beneficial effect：The lithium ion battery negative material oxygen for the long circulating high magnification electrochemical performance that the present invention is provided
The preparation method of graphite controls reaction condition to realize optimization of electrode material by adjusting strong acid and oxidant and graphite ratio
Expect the purpose of chemical property, method is simple, technique is controllable, there is the negative material of acquisition good chemical property, length to follow
Ring stability is high, high rate performance is good, safe and reliable, the need for effectively meeting lithium ion battery.Current few people's research is not
Graphite oxide with degree of oxidation is applied in lithium battery directly as negative material, obtains optimal high-rate charge-discharge capability
Negative material.
Brief description of the drawings
Fig. 1 is compared to prepare product in example 2 below with the cycle performance of graphite powder.
Fig. 2 is compared to prepare product in example 2 below with the high rate performance of graphite powder.
Fig. 3 is compared to prepare product in example 2 below with the high-multiplying power discharge specific capacity of graphite powder.
Embodiment
Illustrated according to encompassed content
Embodiment 1：
1) graphite powder and concentrated sulfuric acid dispensing are subjected to low-temp reaction 2 minutes at 0 degree, Gao Meng is then slowly added to while stirring
Sour potassium, in low temperature, 0 degree is reacted 0.5 hour.The mass ratio of the concentrated sulfuric acid and potassium permanganate and graphite powder is 11.5:1.75:1.
2) step 1) after the completion of reaction, reactant be warming up to 20 degree carry out middle temperature and react 0.5 hour, addition afterwards go from
Sub- water is warming up to 70 degree of progress high temperature hairs and answered, 0.5 hour reaction time.
3) step 2) product is cooled to after room temperature, and add after the completion of hydrogen peroxide, question response and add warm water suction filtration, and with dilute
Salt acid elution is repeatedly dried in vacuo afterwards.Produce graphite oxide negative material.
Embodiment 2：
1) by graphite powder and concentrated sulfuric acid dispensing in 0 degree progress low-temp reaction 10 minutes, then while stirring 40.25:
6.125:1。
2) step 1) after the completion of reaction, reactant is warming up to 35 degree and carries out middle temperature reaction 2 hours, deionization is added afterwards
Water is warming up to 90 degree of progress high temperature hairs and answered, 1 hour reaction time.
3) step 2) product is cooled to after room temperature, and add after the completion of hydrogen peroxide, question response and add warm water suction filtration, and with dilute
Salt acid elution is repeatedly dried in vacuo afterwards.Produce graphite oxide negative material.
Embodiment 3：
1) by graphite powder and concentrated sulfuric acid dispensing in 10 degree progress low-temp reactions 30 minutes, then while stirring 92:14:1.
2) step 1) after the completion of reaction, reactant is warming up to 50 degree and carries out middle temperature reaction 6 hours, deionization is added afterwards
Water is warming up to 98 degree of progress high temperature hairs and answered, 5 hours reaction time.
3) step 2) product is cooled to after room temperature, and add after the completion of hydrogen peroxide, question response and add warm water suction filtration, and with dilute
Salt acid elution is repeatedly dried in vacuo afterwards.Produce graphite oxide negative material.
Embodiment 3：
1) by graphite powder and concentrated sulfuric acid dispensing in 6 degree progress low-temp reactions 20 minutes, then while stirring 46:7:1.
2) step 1) after the completion of reaction, reactant is warming up to 40 degree and carries out middle temperature reaction 3 hours, deionization is added afterwards
Water is warming up to 85 degree of progress high temperature hairs and answered, 3 hours reaction time.
3) step 2) product is cooled to after room temperature, and add after the completion of hydrogen peroxide, question response and add warm water suction filtration, and with dilute
Salt acid elution is repeatedly dried in vacuo afterwards.Produce graphite oxide negative material.
Claims (6)
1. a kind of preparation method of the graphite oxide negative material of high performance lithium ion battery, it is characterised in that：This method includes
Following steps：
Step 1) graphite powder and strong acid dispensing are subjected to low-temp reaction, oxidant is then slowly added to while stirring, it is anti-in low temperature
Should a period of time；
Step 2) by step 1) reactant carry out middle temperature and react, deionized water progress pyroreaction is added afterwards；
Step 3) step 2) reaction product be cooled to after room temperature, add hydrogen peroxide, warm water suction filtration added after the completion of question response,
And be dried in vacuo after being washed with watery hydrochloric acid repeatedly, produce graphite oxide negative material.
2. the preparation method of the graphite oxide negative material of high performance lithium ion battery according to claim 1, its feature
It is：In step 1) in, the strong acid is the concentrated sulfuric acid, and oxidant is potassium permanganate.
3. the preparation method of the graphite oxide negative material of high performance lithium ion battery according to claim 1, its feature
It is：Step 1) in, the mass ratio of the strong acid and oxidant and graphite is：23x:3.5x:1, wherein 0.5<x<4.
4. the preparation method of the graphite oxide negative material of high performance lithium ion battery according to claim 1, its feature
It is：Step 1) in, low-temp reaction whipping temp is 0-10 DEG C, and 2-30 minute sulfuric acid reaction time, is added after oxidant instead
It is 0.5-6 hours between seasonable.
5. the preparation method of the graphite oxide negative material of high performance lithium ion battery according to claim 1, its feature
It is：Step 2) in, middle temperature reaction temperature is 20-50 degree, and the reaction time is 0.5-6 hours.
6. the preparation method of the graphite oxide negative material of high performance lithium ion battery according to claim 1, its feature
It is：Pyroreaction temperature is 70-98 DEG C, and the time is 0.5-5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832087A (en) * | 2018-06-08 | 2018-11-16 | 湖南大学 | A kind of cell negative electrode material and preparation method thereof |
| CN110817836A (en) * | 2019-11-12 | 2020-02-21 | 东海县博汇新材料科技有限公司 | Method for preparing low-temperature lithium ion battery negative electrode material from graphene residual carbon |
| CN110894070A (en) * | 2019-12-06 | 2020-03-20 | 中国科学院山西煤炭化学研究所 | Device and method for continuously preparing graphite oxide |
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| CN104051160A (en) * | 2014-05-30 | 2014-09-17 | 大英聚能科技发展有限公司 | Graphene for electrical double-layer capacitor and preparation method thereof |
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| CN104860302A (en) * | 2015-04-28 | 2015-08-26 | 南京信息工程大学 | Preparation method of wide interlayer spacing and easily-striping graphite oxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832087A (en) * | 2018-06-08 | 2018-11-16 | 湖南大学 | A kind of cell negative electrode material and preparation method thereof |
| CN108832087B (en) * | 2018-06-08 | 2021-04-30 | 湖南大学 | Battery negative electrode material and preparation method thereof |
| CN110817836A (en) * | 2019-11-12 | 2020-02-21 | 东海县博汇新材料科技有限公司 | Method for preparing low-temperature lithium ion battery negative electrode material from graphene residual carbon |
| CN110894070A (en) * | 2019-12-06 | 2020-03-20 | 中国科学院山西煤炭化学研究所 | Device and method for continuously preparing graphite oxide |
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Application publication date: 20170922 |