CN103730631B - A kind of lithium ion battery cathode material and its preparation method - Google Patents

A kind of lithium ion battery cathode material and its preparation method Download PDF

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Publication number
CN103730631B
CN103730631B CN201310696665.6A CN201310696665A CN103730631B CN 103730631 B CN103730631 B CN 103730631B CN 201310696665 A CN201310696665 A CN 201310696665A CN 103730631 B CN103730631 B CN 103730631B
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lithium ion
ion battery
attapulgite
hours
native graphite
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CN103730631A (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

A kind of lithium ion battery negative material, be prepared from by through the native graphite of physics and chemistry method process and heat-treated attapulgite, mass ratio is 0-0.4:1; A kind of preparation method of lithium ion battery negative material, comprise the following steps, step one, physics and chemistry process is carried out to native graphite: by native graphite by high energy ball mill dispersion 2-10 hour, then add in 30%-50% sulfuric acid solution, at 10-50 DEG C, process 8-22 hour, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder having nano-pore; Step 2, by attapulgite 100 DEG C of-500 DEG C of heat treated 10-15 hour in air dry oven; Step 3, stirs 10-15 hour by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained lithium ion battery negative 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, particularly relate to a kind of lithium ion battery cathode material and its preparation method.
Background technology
Lithium ion battery has the advantages such as high power capacity, high output voltage, high-energy-density, memory-less effect and non-environmental-pollution compared with traditional secondary cell.Can as the power supply of the electronic products such as mobile phone, notebook computer, camera, computer.
For improving the performance of lithium ion battery further, 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 the process of physics and chemistry method, as the negative material of lithium ion battery, poor with the adhesive property of collector, in cycle charge discharge electric process, carbon negative pole material is easier 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) JournalofPowerSources68187 (1997) JournalofPowerSources68291 (1997)], especially reduce useful life during 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: being prepared from by through the native graphite of physics and chemistry method process and heat-treated attapulgite, is 0-0.4:1 through the native graphite of physics and chemistry method process and the mass ratio of heat-treated attapulgite;
In this material, be 0.33:1 through the native graphite of physics and chemistry method process and the mass ratio of heat-treated attapulgite;
A preparation method for lithium ion battery negative material, comprises the following steps, and it is characterized in that:
Step one, physics and chemistry process is carried out to native graphite: by native graphite by high energy ball mill dispersion 2-10 hour, then add in 30%-50% sulfuric acid solution, at 10-50 DEG C, process 8-22 hour, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder having nano-pore;
Step 2, by attapulgite 100 DEG C of-500 DEG C of heat treated 10-15 hour in air dry oven;
Step 3, stirs 10-15 hour by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained lithium ion battery negative material.
In the method,
Step one, disperses 2 hours by 60g native graphite by high energy ball mill, then joins in 200g30% sulfuric acid solution, processes 20 hours, filter, be diluted to neutrality at 20 DEG C, and drying preparation becomes the graphite composite powder having nano-pore;
Step 2, by 40g attapulgite 400 DEG C of heat treated 15 hours in air dry oven;
Step 3, stirs 10 hours by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained lithium ion battery negative material;
In the method,
Step one, first disperses 4 hours by 80g native graphite by high energy ball mill, then joins in 300g30% sulfuric acid solution, processes 10 hours, filter, be diluted to neutrality at 50 DEG C, and drying preparation becomes the graphite composite powder having nano-pore.
Step 2, by 20g attapulgite 300 DEG C of heat treated 10 hours in air dry oven;
Step 3, stirs 15 hours by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained lithium ion battery negative material.
In the method,
Step one, disperses 4 hours by 90g native graphite by high energy ball mill, then joins in 300g30% sulfuric acid solution, processes 10 hours, filter, be diluted to neutrality at 50 DEG C, and drying preparation becomes the graphite composite powder having nano-pore;
Step 2, by 10g attapulgite 200 DEG C of heat treated 12 hours in air dry oven;
Step 3, stirs 13 hours by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained lithium ion battery negative material.
Advantageous effect of the present invention is: owing to employing method of the present invention, so the product produced has the following advantages, (1) improves the caking property of carbon negative pole material and collector; (2) capacity of lithium ion battery improves 5%-10%; (3) cycle life of lithium ion battery improves 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 high energy ball mill high speed dispersion 2 hours, then join in 200g30% sulfuric acid solution, process 20 hours, filter, be diluted to neutrality at 20 DEG C, drying preparation becomes the graphite composite powder having nano-pore; 2, the process of attapulgite: by 40g attapulgite 400 DEG C of heat treated 15 hours in air dry oven; 3, by the above-mentioned attapulgite through high-temperature process with stir 10 hours through the native graphite of physico-chemical process process, mix, obtained lithium ion battery negative material.
Embodiment 2
1, first 80g native graphite is passed through high energy ball mill high speed dispersion 4 hours, then join in 300g30% sulfuric acid solution, process 10 hours, filter, be diluted to neutrality at 50 DEG C, drying preparation becomes the graphite composite powder having nano-pore; 2, the process of attapulgite: by 20g attapulgite in air dry oven 300 DEG C heating 10 hours; 3, the native graphite of the above-mentioned attapulgite through high-temperature process and physico-chemical process process is stirred 10 hours, mix, obtained lithium ion battery negative material.
Embodiment 3
1, first 90g native graphite is passed through high energy ball mill high speed dispersion 4 hours, then join in 300g30% sulfuric acid solution, process 10 hours, filter, be diluted to neutrality at 50 DEG C, drying preparation becomes the graphite composite powder having nano-pore; 2, the process of attapulgite: by 10g attapulgite 200 DEG C 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 process is stirred 13 hours, mix, obtained lithium ion battery negative material.
Comparative example 4
First 100g native graphite is passed through high energy ball mill high speed dispersion 2 hours, then join in 300g30% sulfuric acid solution, 20 hours are processed at 20 DEG C, filter, be diluted to neutrality, dry preparation and become the graphite composite powder having nano-pore, the lithium ion battery negative material that it can be used as the negative material of lithium ion battery above-mentioned various method to be prepared and thickener (sodium carboxymethylcellulose--CMC), solvent (deionized water), adhesive (butadiene-styrene rubber--SBR) and conductive agent (conductive black--Super-P) etc. make cathode size; Utilize tertiary cathode material (Li(NiCoMn) O2), solvent (1-METHYLPYRROLIDONE--NMP), binding agent (Kynoar--PVDF) and conductive agent (conductive black--Super-P) etc. be prepared into anode sizing agent.Being made negative plate and the positive plate of lithium ion battery respectively by lithium ion production technology, is barrier film with microporous polypropylene membrane, with LiPF 6for electrolyte, the solution formed for solvent with ethylene carbonate, dimethyl carbonate and diethyl carbonate is assembled into lithium ion battery for electrolyte.
Lithium ion battery negative material the present invention prepared and positive electrode, barrier film and electrolyte are assembled into lithium ion battery.
Attapulgite has unique dispersion, high temperature resistant, anti-good colloidal nature and the higher adsorption bleaching ability such as saline and alkaline.And there 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 time wet, dry after-contraction is little, and not quite aobvious crackle, suspension meets dielectric not flocculation sediment.After high-temperature process, itself and the native graphite through the process of 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 capacity and the cycle charge discharge electric life of adhesive property between carbon negative electrode material of lithium ion cell and collector and lithium ion battery.

Claims (6)

1. a lithium ion battery negative material, it is characterized in that: being prepared from by through the native graphite of physics and chemistry method process and heat-treated attapulgite, is 0-0.4:1 through the native graphite of physics and chemistry method process and the mass ratio of heat-treated attapulgite.
2. a kind of lithium ion battery negative material according to claim 1, is characterized in that: be 0.33:1 through the native graphite of physics and chemistry method process and the mass ratio of heat-treated attapulgite.
3. the preparation method of a kind of lithium ion battery negative material according to claim 1 and 2, comprises the following steps, it is characterized in that:
Step one, physics and chemistry process is carried out to native graphite: by native graphite by high energy ball mill dispersion 2-10 hour, then add in 30%-50% sulfuric acid solution, at 10-50 DEG C, process 8-22 hour, filter, be diluted to neutrality, drying preparation becomes the graphite composite powder having nano-pore;
Step 2, by attapulgite 100 DEG C of-500 DEG C of heat treated 10-15 hour in air dry oven;
Step 3, stirs 10-15 hour by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained 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, it is characterized in that:
Step one, disperses 2 hours by 60g native graphite by high energy ball mill, then joins in 200g30% sulfuric acid solution, processes 20 hours, filter, be diluted to neutrality at 20 DEG C, and drying preparation becomes the graphite composite powder having nano-pore;
Step 2, by 40g attapulgite 400 DEG C of heat treated 15 hours in air dry oven;
Step 3, stirs 10 hours by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained lithium ion battery negative material.
5. the preparation method of a kind of lithium ion battery negative material according to claim 3, comprises the following steps, it is characterized in that:
Step one, first disperses 4 hours by 80g native graphite by high energy ball mill, then joins in 300g30% sulfuric acid solution, processes 10 hours, filter, be diluted to neutrality at 50 DEG C, and drying preparation becomes the graphite composite powder having nano-pore;
Step 2, by 20g attapulgite 300 DEG C of heat treated 10 hours in air dry oven;
Step 3, stirs 15 hours by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained lithium ion battery negative material.
6. the preparation method of a kind of lithium ion battery negative material according to claim 3, comprises the following steps, it is characterized in that:
Step one, disperses 4 hours by 90g native graphite by high energy ball mill, then joins in 300g30% sulfuric acid solution, processes 10 hours, filter, be diluted to neutrality at 50 DEG C, and drying preparation becomes the graphite composite powder having nano-pore;
Step 2, by 10g attapulgite 200 DEG C of heat treated 12 hours in air dry oven;
Step 3, stirs 13 hours by the native graphite of step one physics and chemistry process and step 2 through the attapulgite of heat treated, mixes, obtained 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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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
CN111137924B (en) * 2018-11-06 2022-05-03 清华大学 Negative electrode active material, preparation method thereof, electrochemical cell negative electrode material and electrochemical cell

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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

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Publication number Priority date Publication date Assignee Title
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

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Address before: 277800 Shandong Zaozhuang high tech Zone Thailand Industrial Park Fuyuan five road hight Electronics Group

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