CN103730631A - Lithium ion battery anode material and preparation method thereof - Google Patents

Lithium ion battery anode material and preparation method thereof Download PDF

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Publication number
CN103730631A
CN103730631A CN201310696665.6A CN201310696665A CN103730631A CN 103730631 A CN103730631 A CN 103730631A CN 201310696665 A CN201310696665 A CN 201310696665A CN 103730631 A CN103730631 A CN 103730631A
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hours
lithium ion
ion battery
attapulgite
native graphite
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CN201310696665.6A
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CN103730631B (en
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关成善
宗继月
李涛
单传省
贾传龙
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Shandong Goldencell Electronics Technology Co Ltd
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Shandong Goldencell Electronics Technology Co Ltd
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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
    • 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
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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 lithium ion battery anode material which is prepared from natural graphite treated by physical and chemical methods and attapulgite subjected to heating treatment, wherein a mass ratio of the natural graphite to the attapulgite is (0-0.4):1. The method for preparing the lithium ion battery anode material comprises the following steps: 1, performing physical and chemical treatment on the natural graphite, dispersing the natural graphite for 2-10 hours through a high energy ball mill, adding the natural graphite into a 30-50 percent of sulfuric acid solution, treating at the temperature of 10-50 DEG C for 8-22 hours, filtering, diluting to be neutral, drying and preparing graphite powder with nano pores; 2, performing heating treatment on the attapulgite in an air dry oven at the temperature of 100-500 DEG C for 10-15 hours; 3, stirring the natural graphite subjected to the physical and chemical treatment in the step 1 and the attapulgite subjected to the heating treatment in the step 2 for 10-15 hours, uniformly mixing, and preparing the lithium ion battery anode material.

Description

A kind of lithium ion battery cathode material and its preparation method
Technical field
The present invention relates to a kind of negative material and preparation method thereof, relate in particular to a kind of lithium ion battery cathode material and its preparation method.
Background technology
Lithium ion battery compare with traditional secondary cell there is high power capacity, the advantage such as high output voltage, high-energy-density, memory-less effect and non-environmental-pollution.Can be used as the power supply of the electronic products such as mobile phone, notebook computer, camera, computer.
For further improving the performance of lithium ion battery, people conduct in-depth research carbon negative pole material.Traditional lithium ion battery negative material has graphite, acetylene black, microporous carbon, petroleum coke, polymer pyrolysis and carbon nano-tube etc.By native graphite and all kinds of material with carbon element after physics and chemistry method is processed, negative material as lithium ion battery, poor with the adhesive property of collector, in cycle charge discharge electric process, carbon negative pole material more easily comes off from collection liquid surface, causes lithium ion battery chemical property poor short with useful life.[J.Electrochem.Soc., 144 (4) 1195 (1997) J.Electrochem.Soc., 146 (11) 3963 (1999) Journal of Power Sources 68 187 (1997) Journal of Power Sources 68 291 (1997)], the useful life while especially having reduced high current charge-discharge.
Summary of the invention
The object of this invention is to provide and a kind ofly can improve the adhesive property of carbon negative electrode material of lithium ion cell in coating process and between collector, improve the capacity of lithium ion battery and a kind of lithium ion battery cathode material and its preparation method of service life cycle.
Another object of the present invention is to provide a kind of preparation method of lithium ion battery negative material.
For achieving the above object, the technical solution used in the present invention is: a kind of lithium ion battery negative material, it is characterized in that: by the native graphite of processing through physics and chemistry method and heat-treated attapulgite, be prepared from, the mass ratio of the native graphite of processing through physics and chemistry method and heat-treated attapulgite is 0-0.4:1;
In this material, the mass ratio of the native graphite of processing through physics and chemistry method and heat-treated attapulgite is 0.33:1;
A preparation method for lithium ion battery negative material, comprises the following steps, and it is characterized in that:
Step 1, native graphite is carried out to physics and chemistry processing: native graphite is disperseed to 2-10 hour by high energy ball mill, then add in 30%-50% sulfuric acid solution, at 10-50 ℃, process 8-22 hour, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder that has nano-pore;
Step 2, by attapulgite 100 ℃ of-500 ℃ of heat treated 10-15 hour in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 10-15 hour through the attapulgite of heat treated, mix, and make lithium ion battery negative material.
In the method,
Step 1, disperses 60g native graphite 2 hours by high energy ball mill, then joins in 200g 30% sulfuric acid solution, processes 20 hours at 20 ℃, filters, is diluted to neutrality, and drying preparation becomes the graphite composite powder that has nano-pore;
Step 2, by 40g attapulgite 400 ℃ of heat treated 15 hours in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 10 hours through the attapulgite of heat treated, mix, and make lithium ion battery negative material;
In the method,
Step 1, first disperses 80g native graphite 4 hours by high energy ball mill, then joins in 300g 30% sulfuric acid solution, processes 10 hours at 50 ℃, filters, is diluted to neutrality, and drying preparation becomes the graphite composite powder that has nano-pore.
Step 2, by 20g attapulgite 300 ℃ of heat treated 10 hours in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 15 hours through the attapulgite of heat treated, mix, and make lithium ion battery negative material.
In the method,
Step 1, disperses 90g native graphite 4 hours by high energy ball mill, then joins in 300g 30% sulfuric acid solution, processes 10 hours at 50 ℃, filters, is diluted to neutrality, and drying preparation becomes the graphite composite powder that has nano-pore;
Step 2, by 10g attapulgite 200 ℃ of heat treated 12 hours in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 13 hours through the attapulgite of heat treated, mix, and make lithium ion battery negative material.
Advantageous effect of the present invention is: owing to having used method of the present invention, so the product of producing has the following advantages, (1) has improved the caking property of carbon negative pole material and collector; (2) capacity of lithium ion battery has improved 5%-10%; (3) cycle life of lithium ion battery has improved 10%-30%.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
1, first 60g native graphite is passed through to high energy ball mill high speed dispersion 2 hours, then join in 200g 30% sulfuric acid solution, process 20 hours at 20 ℃, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder that has nano-pore; 2, the processing of attapulgite: by 40g attapulgite 400 ℃ of heat treated 15 hours in air dry oven; 3, the above-mentioned native graphite that passes through the attapulgite of high-temperature process and process through physico-chemical process is stirred 10 hours, mix, make lithium ion battery negative material.
Embodiment 2
1, first 80g native graphite is passed through to high energy ball mill high speed dispersion 4 hours, then join in 300g 30% sulfuric acid solution, process 10 hours at 50 ℃, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder that has nano-pore; 2, the processing of attapulgite: by 20g attapulgite in air dry oven 300 ℃ heating 10 hours; 3, the native graphite of the above-mentioned attapulgite through high-temperature process and physico-chemical process processing is stirred 10 hours, mix, make lithium ion battery negative material.
Embodiment 3
1, first 90g native graphite is passed through to high energy ball mill high speed dispersion 4 hours, then join in 300g 30% sulfuric acid solution, process 10 hours at 50 ℃, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder that has nano-pore; 2, the processing of attapulgite: by 10g attapulgite 200 ℃ of heat treated 12 hours in air dry oven; 3, the native graphite of the above-mentioned attapulgite through high-temperature process and physico-chemical process processing is stirred 13 hours, mix, make lithium ion battery negative material.
Comparative example 4
First 100g native graphite is passed through to high energy ball mill high speed dispersion 2 hours, then join in 300g 30% sulfuric acid solution, at 20 ℃, process 20 hours, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder that has nano-pore, and (--CMC), (butadiene-styrene rubber--SBR) and conductive agent (conductive black--Super-P) etc. is made cathode size to sodium carboxymethylcellulose for solvent (deionized water), adhesive for the lithium ion battery negative material that the negative material using it as lithium ion battery is prepared above-mentioned the whole bag of tricks and thickener; Utilize tertiary cathode material (Li(NiCoMn) O2), (--NMP), (Kynoar--PVDF) and conductive agent (conductive black--Super-P) etc. is prepared into anode sizing agent to binding agent to 1-METHYLPYRROLIDONE to solvent.By lithium ion production technology, make respectively negative plate and the positive plate of lithium ion battery, take microporous polypropylene membrane as barrier film, with LiPF 6for electrolyte, the solution that ethylene carbonate, dimethyl carbonate and diethyl carbonate be that solvent forms of take is assembled into lithium ion battery as electrolyte.
Lithium ion battery negative material prepared by the present invention and positive electrode, barrier film and electrolyte are assembled into lithium ion battery.
Attapulgite has unique dispersion, high temperature resistant, the anti-good colloidal nature such as saline and alkaline and higher adsorption bleaching ability.And thering is certain plasticity and cohesive force, its desirable chemical molecular formula is: Mg 5si 8o 20(OH) 2(OH 2) 44H 2o.There is the intermediate structure between chain structure and layer structure.Tool viscosity and plasticity when wet, dry after-contraction is little, not quite aobvious crackle, suspension is met not flocculation sediment of dielectric.After high-temperature process, itself and the native graphite processed through physics and chemistry method are stirred, attapulgite and the graphite material mass ratio with nano-pore are 0-0.33:1.Adopt lithium ion battery negative material of the present invention can improve adhesive property between carbon negative electrode material of lithium ion cell and collector and capacity and the cycle charge discharge electric life of lithium ion battery.

Claims (6)

1. a lithium ion battery negative material, it is characterized in that: by the native graphite of processing through physics and chemistry method and heat-treated attapulgite, be prepared from, the mass ratio of the native graphite of processing through physics and chemistry method and heat-treated attapulgite is 0-0.4:1.
2. a kind of lithium ion battery negative material according to claim 1, is characterized in that: the mass ratio of the native graphite of processing through physics and chemistry method and heat-treated attapulgite is 0.33:1.
3. the preparation method of a kind of lithium ion battery negative material according to claim 1 and 2, comprises the following steps, and it is characterized in that:
Step 1, native graphite is carried out to physics and chemistry processing: native graphite is disperseed to 2-10 hour by high energy ball mill, then add in 30%-50% sulfuric acid solution, at 10-50 ℃, process 8-22 hour, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder that has nano-pore;
Step 2, by attapulgite 100 ℃ of-500 ℃ of heat treated 10-15 hour in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 10-15 hour through the attapulgite of heat treated, mix, and make lithium ion battery negative material.
4. the preparation method of a kind of lithium ion battery negative material according to claim 3, comprises the following steps, and it is characterized in that:
Step 1, disperses 60g native graphite 2 hours by high energy ball mill, then joins in 200g 30% sulfuric acid solution, processes 20 hours at 20 ℃, filters, is diluted to neutrality, and drying preparation becomes the graphite composite powder that has nano-pore;
Step 2, by 40g attapulgite 400 ℃ of heat treated 15 hours in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 10 hours through the attapulgite of heat treated, mix, and make lithium ion battery negative material.
5. the preparation method of a kind of lithium ion battery negative material according to claim 4, comprises the following steps, and it is characterized in that:
Step 1, first disperses 80g native graphite 4 hours by high energy ball mill, then joins in 300g 30% sulfuric acid solution, processes 10 hours at 50 ℃, filters, is diluted to neutrality, and drying preparation becomes the graphite composite powder that has nano-pore;
Step 2, by 20g attapulgite 300 ℃ of heat treated 10 hours in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 15 hours through the attapulgite of heat treated, mix, and make lithium ion battery negative material.
6. the preparation method of a kind of lithium ion battery negative material according to claim 5, comprises the following steps, and it is characterized in that:
Step 1, disperses 90g native graphite 4 hours by high energy ball mill, then joins in 300g 30% sulfuric acid solution, processes 10 hours at 50 ℃, filters, is diluted to neutrality, and drying preparation becomes the graphite composite powder that has nano-pore;
Step 2, by 10g attapulgite 200 ℃ of heat treated 12 hours in air dry oven;
Step 3, the native graphite that step 1 physics and chemistry is processed and step 2 stir 13 hours through the attapulgite of heat treated, mix, and make lithium ion battery negative material.
CN201310696665.6A 2013-12-18 2013-12-18 A kind of lithium ion battery cathode material and its preparation method Active CN103730631B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103803948A (en) * 2014-03-21 2014-05-21 枣庄市明通新型建材有限公司 Preparation method of urban sludge added sintered bricks
CN107393630A (en) * 2017-07-19 2017-11-24 安徽国电电缆股份有限公司 A kind of preparation method with conductive and antibacterial cable attapulgite composite material
CN110504449A (en) * 2018-05-17 2019-11-26 清华大学 Class palygorskite material, negative electrode active material and preparation method thereof, electrochemical cell negative electrode material and electrochemical cell
CN111137924A (en) * 2018-11-06 2020-05-12 清华大学 Negative electrode active material, preparation method thereof, electrochemical cell negative electrode material and electrochemical cell

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002013304A1 (en) * 2000-08-04 2002-02-14 Southern Clay Products, Inc. Gelled anode or electrolyte solution for an electrochemical cell
KR100788211B1 (en) * 2006-12-21 2007-12-26 한국화학연구원 Polymer electrolyte composite materials including organic clay and lithium secondary battery comprising same
CN103066299A (en) * 2013-01-08 2013-04-24 东莞新能源科技有限公司 Modified natural graphite coated with borosilicate, and its preparation method
CN103236545A (en) * 2013-04-12 2013-08-07 东莞新能源科技有限公司 Natural graphite with coating modification and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002013304A1 (en) * 2000-08-04 2002-02-14 Southern Clay Products, Inc. Gelled anode or electrolyte solution for an electrochemical cell
KR100788211B1 (en) * 2006-12-21 2007-12-26 한국화학연구원 Polymer electrolyte composite materials including organic clay and lithium secondary battery comprising same
CN103066299A (en) * 2013-01-08 2013-04-24 东莞新能源科技有限公司 Modified natural graphite coated with borosilicate, and its preparation method
CN103236545A (en) * 2013-04-12 2013-08-07 东莞新能源科技有限公司 Natural graphite with coating modification and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103803948A (en) * 2014-03-21 2014-05-21 枣庄市明通新型建材有限公司 Preparation method of urban sludge added sintered bricks
CN103803948B (en) * 2014-03-21 2016-01-06 枣庄市明通新型建材有限公司 A kind of preparation method adding city sludge vitrified brick
CN107393630A (en) * 2017-07-19 2017-11-24 安徽国电电缆股份有限公司 A kind of preparation method with conductive and antibacterial cable attapulgite composite material
CN110504449A (en) * 2018-05-17 2019-11-26 清华大学 Class palygorskite material, negative electrode active material and preparation method thereof, electrochemical cell negative electrode material and electrochemical cell
CN111137924A (en) * 2018-11-06 2020-05-12 清华大学 Negative electrode active material, preparation method thereof, electrochemical cell negative electrode material and electrochemical cell

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