CN105336911A - Method for coating and modifying lithium ion battery graphite negative electrode material with lignin - Google Patents
Method for coating and modifying lithium ion battery graphite negative electrode material with lignin Download PDFInfo
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- CN105336911A CN105336911A CN201510233628.0A CN201510233628A CN105336911A CN 105336911 A CN105336911 A CN 105336911A CN 201510233628 A CN201510233628 A CN 201510233628A CN 105336911 A CN105336911 A CN 105336911A
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- lignin
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/5835—Comprising fluorine or fluoride salts
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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 method for modifying a lithium ion battery graphite negative electrode. The method is characterized in that lignin is adopted as a coating material to improve the performances of a graphite negative electrode material, and the method comprises the following steps: dissolving lignin in an alkali solution, coating graphite powder, crushing the obtained coated material, screening the crushed coated material, and carrying out high temperature charring. The graphite negative electrode composite material prepared in the invention has the advantages of increased tap density, decreased specific surface area, improved initial charge-discharge efficiency, irreversible capacity and other performances, and no pollution to environment.
Description
Technical field
The present invention relates to a kind of method of modifying improving graphite negative material of lithium ion battery performance, it is characterized in that adopting lignin as coating modification material.
Background technology
At present, the negative material of commercial lithium-ion batteries mainly graphite-based powdery material with carbon element.Graphite is due to good conductivity, and degree of crystallinity is higher, has the advantages such as good layer structure, becomes the carbon negative pole material that the current Application comparison of lithium ion battery is general.
But, graphite is as carbon negative electrode material of lithium ion cell, in use remain and need to improve in following problem, such as, in the charge and discharge process of lithium ion turnover graphite linings, graphite-structure expands repeatedly and shrinks, in electrolyte, solvent easily enters graphite linings generation solvent thereupon and embeds phenomenon altogether embedding lithium ability is reduced, and easily make graphite flake be peeling, cause electrode charge and discharge capacity to decline, cycle charge discharge electrical stability and useful life decline; In addition, the profile through fragmentation processing, screening graphite pulverulent material is out irregular, and specific area is large and tap density is lower, and the first charge-discharge efficiency of graphite electrode material also can be caused lower.
Research finds, at graphite granule Surface coating one deck amorphous carbon, contributes to improving its tap density, reduces specific area, thus improves the chemical property of graphite electrode material.Liquid phase coating method is one of common method of modified graphite, is dissolved in for carrying out coated to graphite in liquid-phase system by amorphous carbon persursor material, through mixing coated, dehydrate and heat the steps such as charing and complete modification.At present, conventional coated presoma has the polymer such as pitch, epoxy resin, phenolic resins, the chemical property of graphite cathode material can be made to have corresponding improvement through coated carbonization treatment.Chinese patent CN101604748B discloses a kind of method that low temperature pyrogenation graphite covered by asphalt prepares high rate lithium ionic cell cathode material, the method adds graphitization catalyst in pitch, improve the degree of graphitization of pyrolyzed bitumen, modified graphite material chemical property is improved.Mesophase pitch is carried out photoelectric elements by Chinese patent CN101286556B; and by nanojet device, the mesophase pitch in semi-liquid stage is ejected into graphite surface; it is evenly coated that this method can realize graphite; but preparation cost is higher; and condition is difficult to control, and is unfavorable for large-scale production.Pitch and resin are dissolved in organic solvent by Chinese patent CN102910618A and Chinese patent CN1304187A respectively, mix with graphite carry out coated with high temperature cabonization process, covered effect is good, improve particle uniformity and the charge-discharge performance of graphite, but dissolved bitumen needs the organic solvent such as benzene, toluene, not only cost is high, and easily causes environmental pollution.
Summary of the invention
The object of this invention is to provide a kind of take lignin as the method for modifying of the silicon/carbon/graphite in lithium ion batteries material of coated presoma.Lignin is natural polymers, wide material sources, low price, and is soluble in alkaline aqueous solution, and high temperature cabonization carbon yield is high, therefore can complete coated in water solution system, without organic solvent, and environmentally safe.Graphite composite material tap density after lignin coating modification increases, and specific area reduces, and the performance such as first charge-discharge efficiency and irreversible capacity significantly improves.
The method of lignin modification graphite cathode material provided by the invention, comprises the steps:
(1) graphite powder of particle diameter <25 μm be impregnated in the lignin liquor dissolved with alkali lye;
(2) stir graphite powder is fully mixed with lignin alkali lye, then heat up dehydration, obtains the solid mixture of lignin coated graphite powder, then pulverize, sieve out the lignin coating modification graphite cathode material presoma that average grain diameter is 15 ~ 25 μm;
(3) coating modification graphite cathode material presoma is placed on by N
2be heated to 700 ° of C ~ 1000 ° C, carbonization 1 ~ 5h in the electrothermal furnace of the inert gas shieldings such as gas or Ar gas, be then cooled to normal temperature, sieve out the lignin coating modification graphite cathode material meeting graphite cathode material granularity requirements.
Wherein, the graphite powder described in step (1) is the one of native graphite, Delanium or carbonaceous mesophase spherules, aqueous slkali be the lithium hydroxide of PH >=12, NaOH, potassium hydroxide aqueous solution any one, first-selected lithium hydroxide.
It is one or more of the depolymerization lignin of 500 ~ 3000 that lignin described in step (1) comprises alkali lignin, lignosulfonates, Milled wood lignin, enzymolysis xylogen and the lignin remaining molecules amount after chemical method or electrochemical process depolymerization process.The mass ratio of graphite powder and lignin is preferably 80:20 ~ 95:5, and that better is 90:10 ~ 95:5.
Beneficial effect of the present invention is as follows:
Utilize preparation method provided by the invention, lignin is coated on graphite surface, and the specific area of composite material obtained after charing is significantly reduced, and tap density also increases, button cell capacity reaches 362mAh/g, and first charge-discharge efficiency reaches 95%.As can be seen here, the electro-chemical properties of graphite composite material prepared by the lignin that the present invention is used obtains effective improvement.
Good effect of the present invention is:
The present invention's lignin is as the carbon precursor of coated graphite, and its carbon yield is high, and abundant raw material source is cheap, effectively can reduce production cost, and preparation process environmentally safe.Specific area and the chemical property of the graphite cathode material of preparation also can effectively be improved.
Embodiment:
Below by specific embodiment, the present invention is described in detail, but the present invention is not limited in the scope of described embodiment.It should be pointed out that without departing from the inventive concept of the premise, some conditions that the present invention makes are changed, all belongs to protection scope of the present invention.
Embodiment 1
Take 6g straw lignin and be placed in 30mL deionized water, the LiOH solution dripping 1mol/L makes it dissolve completely, adds 94g native graphite (D50=17.1 μm, specific area 7.7m in solution
2/ g); stir and dewater under 80 ° of C water bath condition; after moisture removes completely; solid is pulverized, and with 250 object classifying screen screenings, then solid micro-powder is put into tube furnace; 800 ° of C are risen under nitrogen protection with the heating rate of 5 ° of C/min; and constant temperature 2h, take out after being down to room temperature, the graphite cathode material namely after obtained lignin coating modification.The specific area of this negative material reduces 80%, and its button cell capacity is 348mAh/g, first charge-discharge efficiency 90.3%.
Embodiment 2
Take 8g Corn cob lignin and be placed in 30mL deionized water, the NaOH solution dripping 0.1mol/L makes it dissolve completely, adds 92g native graphite (D50=18.7 μm, specific area 1.77m in solution
2/ g); stir and dewater under 60 ° of C water bath condition; after moisture removes completely; solid is pulverized, and with 250 object classifying screen screenings, then solid micro-powder is put into tube furnace; 600 ° of C are risen under nitrogen protection with the heating rate of 10 ° of C/min; and constant temperature 3h, take out after being down to room temperature, the graphite cathode material namely after obtained lignin coating modification.The specific area of this negative material reduces 15%, and its button cell capacity is 355mAh/g, first charge-discharge efficiency 92.5%.
Embodiment 3
Taking 10g sodium lignin sulfonate is dissolved in 100mL deionized water, adds 90g Delanium (D50=17.1 μm, specific area 7.7m in solution
2/ g); stir and dewater under 50 ° of C water bath condition; after moisture removes completely; solid is pulverized, and with 250 object classifying screen screenings, then solid micro-powder is put into tube furnace; 800 ° of C are risen under nitrogen protection with the heating rate of 5 ° of C/min; and constant temperature 2h, take out after being down to room temperature, the graphite cathode material namely after obtained lignin coating modification.The specific area of this negative material reduces 22%, and its button cell capacity is 351mAh/g, first charge-discharge efficiency 88.9%.
Embodiment 4
Take the lignin after 8g electrochemical process depolymerization process, be placed in 30mL deionized water, make it dissolve completely with the LiOH solution of 0.05mol/L, in solution, add 92g native graphite (D50=18.7 μm, specific area 1.77m
2/ g); stir and dewater under 50 ° of C water bath condition; after moisture removes completely; solid is pulverized, and with 250 object classifying screen screenings, then solid micro-powder is put into tube furnace; 800 ° of C are risen under nitrogen protection with the heating rate of 2 ° of C/min; and constant temperature 3h, take out after being down to room temperature, the graphite cathode material namely after obtained lignin coating modification.The specific area of this negative material reduces 11%, and its button cell capacity is 362mAh/g, first charge-discharge efficiency 95.0%.
Claims (5)
1. adopt a method for lignin modification graphite negative material of lithium ion battery, comprise the following steps:
(1) graphite powder of particle diameter <25 μm be impregnated in the lignin liquor dissolved with alkali lye;
(2) stir graphite powder is fully mixed with lignin alkali lye, then heat up dehydration, obtains the solid mixture of lignin coated graphite powder, then pulverize, sieve out the lignin coating modification graphite cathode material presoma that average grain diameter is 15 ~ 25 μm;
(3) coating modification graphite cathode material presoma is placed on by N
2be heated to 700 ° of C ~ 1000 ° C, carbonization 1 ~ 5h in the electrothermal furnace of the inert gas shieldings such as gas or Ar gas, be then cooled to normal temperature, sieve out the lignin coating modification graphite cathode material meeting graphite cathode material granularity requirements.
2. the method for employing lignin modification graphite negative material of lithium ion battery according to claim 1, wherein the graphite powder described in step (1) is the one of native graphite, Delanium or carbonaceous mesophase spherules.
3. the method for employing lignin modification graphite negative material of lithium ion battery according to claim 1, wherein the alkali lye described in step (1) be the NaOH of PH >=12, lithium hydroxide, potassium hydroxide solution any one.
4. the method for employing lignin modification graphite negative material of lithium ion battery according to claim 1, lignin, Milled wood lignin and lignin after wherein the lignin described in step (1) comprises alkali lignin, lignosulfonates, the depolymerization remaining molecules amount after chemical method or electrochemical process depolymerization process is one or more of the depolymerization lignin of 500 ~ 3000.
5. the method for employing lignin modification graphite negative material of lithium ion battery according to claim 1, wherein the graphite powder described in step (1) and lignin quality are than being 80:20 ~ 95:5.
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| CN201510233628.0A CN105336911A (en) | 2015-05-10 | 2015-05-10 | Method for coating and modifying lithium ion battery graphite negative electrode material with lignin |
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| CN201510233628.0A CN105336911A (en) | 2015-05-10 | 2015-05-10 | Method for coating and modifying lithium ion battery graphite negative electrode material with lignin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110085811A (en) * | 2018-04-17 | 2019-08-02 | 南方科技大学 | SiOx/ carbon composite and preparation method thereof, lithium ion battery |
| EP3691000A1 (en) * | 2019-02-01 | 2020-08-05 | Ligna Energy AB | Carbon lignin electrode |
| CN112803008A (en) * | 2021-03-12 | 2021-05-14 | 合肥国轩高科动力能源有限公司 | Preparation method of coated modified high-nickel ternary cathode material and prepared material |
| CN113540449A (en) * | 2021-07-12 | 2021-10-22 | 郑州轻工业大学 | Method for preparing environment-friendly renewable zinc ion battery by grading treatment of crop straws |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323445A (en) * | 2008-06-13 | 2008-12-17 | 东华大学 | Method for preparing porous carbon material based on alkali lignose |
| CN103872330A (en) * | 2014-03-19 | 2014-06-18 | 上海交通大学 | Lithium ion battery negative electrode material and preparation method thereof |
| CN104124431A (en) * | 2014-08-12 | 2014-10-29 | 湖南元素密码石墨烯研究院（有限合伙） | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
| US20150017528A1 (en) * | 2013-07-15 | 2015-01-15 | Clemson University | Polymer-nanocarbon composites, methods of making composites, and energy storage devices including the composite |
-
2015
- 2015-05-10 CN CN201510233628.0A patent/CN105336911A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323445A (en) * | 2008-06-13 | 2008-12-17 | 东华大学 | Method for preparing porous carbon material based on alkali lignose |
| US20150017528A1 (en) * | 2013-07-15 | 2015-01-15 | Clemson University | Polymer-nanocarbon composites, methods of making composites, and energy storage devices including the composite |
| CN103872330A (en) * | 2014-03-19 | 2014-06-18 | 上海交通大学 | Lithium ion battery negative electrode material and preparation method thereof |
| CN104124431A (en) * | 2014-08-12 | 2014-10-29 | 湖南元素密码石墨烯研究院（有限合伙） | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110085811A (en) * | 2018-04-17 | 2019-08-02 | 南方科技大学 | SiOx/ carbon composite and preparation method thereof, lithium ion battery |
| EP3691000A1 (en) * | 2019-02-01 | 2020-08-05 | Ligna Energy AB | Carbon lignin electrode |
| CN112803008A (en) * | 2021-03-12 | 2021-05-14 | 合肥国轩高科动力能源有限公司 | Preparation method of coated modified high-nickel ternary cathode material and prepared material |
| CN112803008B (en) * | 2021-03-12 | 2022-02-01 | 合肥国轩高科动力能源有限公司 | Preparation method of coated modified high-nickel ternary cathode material and prepared material |
| CN113540449A (en) * | 2021-07-12 | 2021-10-22 | 郑州轻工业大学 | Method for preparing environment-friendly renewable zinc ion battery by grading treatment of crop straws |
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