CN107681144A - A kind of preparation method of lithium ion battery negative material - Google Patents
A kind of preparation method of lithium ion battery negative material Download PDFInfo
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- CN107681144A CN107681144A CN201710945811.2A CN201710945811A CN107681144A CN 107681144 A CN107681144 A CN 107681144A CN 201710945811 A CN201710945811 A CN 201710945811A CN 107681144 A CN107681144 A CN 107681144A
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- Prior art keywords
- aluminium
- carbon
- graphite
- coating
- lithium ion
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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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- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 present invention discloses a kind of preparation method of lithium ion battery negative material, and this method first passes through chemical vapour deposition technique and prepares carbon-coating in aluminium surface, and the aluminium of carbon-coating cladding and graphite then are formed into composite, and the mass percent of aluminium powder in the composite is 38 42%.Volume Changes of the aluminium during embedding and removing cause the circulation discharge stability of aluminium poor, graphite in carbon-coating and composite that the present invention is prepared using chemical vapour deposition technique alleviates Volume Changes of the aluminium during embedding and removing, charge-discharge test result shows that aluminium carbon-coating graphite composite material prepared by the present invention has preferably circulation discharge stability.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of preparation method of lithium ion battery negative material.
Background technology
Lithium ion battery is widely used in small-sized movable electronic equipment and electric automobile, mobile electronic device it is multi-functional
Change and the demand for development lithium ion battery energy density of electric automobile constantly rises, can be carried by the specific capacity for improving electrode material
Rise the energy density of battery.The negative pole of commercialized lithium ion battery is mainly graphite cathode, the theoretical discharge ratio of graphite cathode
Capacity is 372mAh/g, and corresponding discharging product is LiC6, the voltage platform of exoelectrical reaction is near 0.1V.The theory of aluminium is put
Electric specific capacity is 2235mAh g-1[Nature Communications,2015,6:7872], corresponding discharging product is
Li9Al4, the voltage platform of exoelectrical reaction is near 0.25V, and the theoretical discharge specific capacity of aluminium is higher than the theoretical discharge ratio of graphite
Capacity, and the discharge voltage plateau of aluminium is close with the discharge voltage plateau of graphite, in addition, aluminium has higher electric conductivity, this makes
It is a kind of negative material with development prospect to obtain aluminium.
In process of intercalation, the Volume Changes of graphite are near 10%, and the Volume Changes of aluminium are near 100%.
During charging and discharging, the Volume Changes of aluminium cause the rupture of surface SEI films, and the SEI films after rupture can regenerate, and this makes
Thickened into SEI films, coulombic efficiency reduce and discharge capacity reduce, SEI films thicken hinder lithium ion migration, this causes to discharge
The reduction of capacity.In addition, the Volume Changes of aluminium destroy the conductive structure of electrode, the electric conductivity and discharge capacity of electrode are reduced.For
Improve the circulation discharge stability of aluminium, it is necessary to alleviate Volume Changes of the aluminium during embedding and removing.
The content of the invention
In order to improve the circulation discharge stability of aluminium, the present invention provides a kind of preparation side of lithium ion battery negative material
Method.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of lithium ion battery negative material, this method first pass through chemical vapour deposition technique in aluminium surface system
Standby carbon-coating, the aluminium of carbon-coating cladding is then formed into composite with graphite, the mass percent of aluminium powder in the composite is 38-
42%, comprise the following steps：
(1) aluminium powder is subjected to ball milling in dispersant, sieved, control aluminum powder particle size D50 is done under the conditions of being less than 1 μm, 50 DEG C
Dry 2h；
(2) aluminium powder is placed in chemical vapor deposition unit, device first is evacuated into air pressure is less than 10Pa, backward device
In be passed through the mixed gas of hydrogen and carbon source, 25-35min is heated at a temperature of 410-450 DEG C, is cooled down, obtains the aluminium of carbon-coating cladding
Powder；
(3) by graphite in dispersant ball milling 2-3h, obtain graphite dispersing solution；
(4) aluminium powder of step (2) carbon-coating cladding, the quality of graphite and the aluminium powder of carbon-coating cladding are added into graphite dispersing solution
Than for (53.3：46.7)-(57.8：42.2), by dispersion liquid ball milling 2.5-3.5h, 2h is dried under the conditions of 50 DEG C, obtain aluminium-carbon-coating-
Graphite composite material.
Further, the dispersant is selected from absolute ethyl alcohol or propyl alcohol.
Further, the chemical vapor deposition unit of the step (2) is selected from hot activation chemical vapor deposition unit, plasma
One kind in body activation chemical vapor deposition unit.
Further, the reaction pressure in the step (2) is 1-2KPa.
Further, carbon source is benzene or toluene in the step (2).
Further, hydrogen and the air pressure of carbon source ratio are 2 in the step (2)：1.
Beneficial effects of the present invention：The present invention first passes through chemical vapour deposition technique and prepares carbon-coating on aluminium powder surface, after by carbon
The aluminium powder of layer cladding forms composite with graphite, and alleviating volume of the aluminium during embedding and removing using carbon-coating and graphite becomes
Change, charge-discharge test result shows, aluminium-carbon-coating-graphite composite material prepared by the present invention has preferably circulation discharge stability
Property.
Brief description of the drawings
Fig. 1 is the initial discharge curve and primary charging song of aluminium-carbon-coating-graphite composite material electrode prepared by embodiment 1
Line；
Fig. 2 is the cyclic curve figure of aluminium-carbon-coating-graphite composite material electrode prepared by embodiment 1.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Aluminium powder (99.9%) is milled to powder granularity D50 less than 1 μm in absolute ethyl alcohol, 2h is dried under the conditions of 50 DEG C
Afterwards, aluminium powder is placed in hot activation chemical vapor deposition unit, it is 9Pa that device first is evacuated into air pressure, and reacting gas is hydrogen
Gas and benzene vapor, benzene vapor are to be carried along into device by hydrogen, after the mixed gas of hydrogen and benzene vapor enters device, by gas
Phase reaction temperature is increased to 450 DEG C, reaction pressure 1kPa, gas phase reaction 35min, and gas passage is closed after the completion of reaction, dress
The aluminium powder that carbon-coating coats is made after putting cooling.By graphite (99.9%) the ball milling 2h in absolute ethyl alcohol, graphite dispersing solution is made, to
The aluminium powder of carbon-coating cladding is added in graphite dispersing solution, the mass ratio for the aluminium powder that graphite coats with carbon-coating is 57.8:42.2, will be scattered
Liquid ball milling 3.5h, after 50 DEG C of dry 2h, aluminium-carbon-coating-graphite composite material, the quality percentage of aluminium powder in the composite is made
Content is 38%.
By aluminium-carbon-coating-graphite composite material and conductive agent (Super P) and adhesive (LA133) using mass ratio as 80：
10：10 are mixed and made into slurries, and after drying process and cutting process, aluminium-carbon-coating-graphite is made coated on copper foil in slurries
Composite electrode, aluminium-carbon-coating-graphite composite material electrode and lithium piece are assembled into button cell in vacuum glove box, passed through
The capacity of test button cell draws the capacity of aluminium-carbon-coating-graphite composite material.Fig. 1 is aluminium-carbon-coating-graphite composite material electricity
The initial discharge curve and primary charging curve of pole, the initial discharge specific capacity of aluminium-carbon-coating-graphite composite material and primary charging
Specific capacity is respectively 710mAh/g and 574mAh/g.Fig. 2 be aluminium-carbon-coating-graphite composite material electrode cyclic curve figure, aluminium-
The circulation discharge stability of carbon-coating-graphite composite material electrode is preferable.
Embodiment 2
Aluminium powder (99.9%) is milled to powder granularity D50 less than 1 μm in propyl alcohol, after drying 2h under the conditions of 50 DEG C,
Aluminium powder is placed in plasma activation chemical vapor deposition unit, it is 7Pa that device first is evacuated into air pressure, and reacting gas is
Hydrogen and toluene vapor, toluene vapor are to be carried along into device by hydrogen, and the mixed gas entrance of hydrogen and toluene vapor fills
Postpone, gas phase reaction temperature is increased to 430 DEG C, reaction pressure 1.5kPa, gas phase reaction 30min, closed after the completion of reaction
Gas passage, the aluminium powder of carbon-coating cladding is made after device cooling.By graphite (99.9%) the ball milling 2.5h in propyl alcohol, graphite is made
Dispersion liquid, the aluminium powder of carbon-coating cladding is added into graphite dispersing solution, the mass ratio for the aluminium powder that graphite coats with carbon-coating is 55.6：
44.4, by dispersion liquid ball milling 3h, after 50 DEG C of dry 2h, aluminium-carbon-coating-graphite composite material is made, aluminium powder is in the composite
Weight/mass percentage composition be 40.4%.
By aluminium-carbon-coating-graphite composite material and conductive agent (Super P) and adhesive (LA133) using mass ratio as 80：
10：10 are mixed and made into slurries, and after drying process and cutting process, aluminium-carbon-coating-graphite is made coated on copper foil in slurries
Composite electrode, aluminium-carbon-coating-graphite composite material electrode and lithium piece are assembled into button cell in vacuum glove box, passed through
The capacity of test button cell draws the capacity of aluminium-carbon-coating-graphite composite material.Charge-discharge test result shows aluminium-carbon-coating-stone
The initial discharge specific capacity and primary charging specific capacity of black composite are respectively 728mAh/g and 585mAh/g.
Embodiment 3
Aluminium powder (99.9%) is milled to powder granularity D50 less than 1 μm in absolute ethyl alcohol, 2h is dried under the conditions of 50 DEG C
Afterwards, aluminium powder is placed in plasma activation chemical vapor deposition unit, it is 5Pa that device first is evacuated into air pressure, reaction gas
Body is hydrogen and benzene vapor, and benzene vapor is to be carried along into device by hydrogen, and the mixed gas of hydrogen and benzene vapor enters device
Afterwards, gas phase reaction temperature is increased to 410 DEG C, reaction pressure 2kPa, gas phase reaction 25min, gas is closed after the completion of reaction
Passage, the aluminium powder of carbon-coating cladding is made after device cooling.By graphite (99.9%) the ball milling 3h in absolute ethyl alcohol, graphite point is made
Dispersion liquid, the aluminium powder of carbon-coating cladding is added into graphite dispersing solution, the mass ratio for the aluminium powder that graphite coats with carbon-coating is 53.3：
46.7, by dispersion liquid ball milling 2.5h, after 50 DEG C of dry 2h, aluminium-carbon-coating-graphite composite material is made, aluminium powder is in composite
In weight/mass percentage composition be 42%.
By aluminium-carbon-coating-graphite composite material and conductive agent (Super P) and adhesive (LA133) using mass ratio as 80：
10：10 are mixed and made into slurries, and after drying process and cutting process, aluminium-carbon-coating-graphite is made coated on copper foil in slurries
Composite electrode, aluminium-carbon-coating-graphite electrode and lithium piece are assembled into button cell in vacuum glove box, by testing button
The capacity of battery draws the capacity of aluminium-carbon-coating-graphite composite material.Charge-discharge test result shows aluminium-carbon-coating-graphite composite wood
The initial discharge specific capacity and primary charging specific capacity of material are respectively 747mAh/g and 594mAh/g.
Claims (6)
1. a kind of preparation method of lithium ion battery negative material, this method first passes through chemical vapour deposition technique and prepared in aluminium surface
Carbon-coating, the aluminium of carbon-coating cladding is then formed into composite with graphite, the mass percent of aluminium powder in the composite is 38-
42%, it is characterised in that comprise the following steps：
（1）Aluminium powder is subjected to ball milling in dispersant, sieved, control aluminum powder particle size D50 dries 2h under the conditions of being less than 1 μm, 50 DEG C；
（2）Aluminium powder is placed in chemical vapor deposition unit, device first is evacuated into air pressure is less than 10Pa, leads in backward device
Enter the mixed gas of hydrogen and carbon source, 25-35min is heated at a temperature of 410-450 DEG C, cool down, obtain the aluminium powder of carbon-coating cladding；
（3）By graphite in dispersant ball milling 2-3h, obtain graphite dispersing solution；
（4）Step is added into graphite dispersing solution（2）The aluminium powder of carbon-coating cladding, the mass ratio for the aluminium powder that graphite coats with carbon-coating are
（53.3：46.7）-（57.8：42.2）, by dispersion liquid ball milling 2.5-3.5h, 2h is dried under the conditions of 50 DEG C, obtains aluminium-carbon-coating-graphite
Composite.
2. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that the dispersant choosing
From absolute ethyl alcohol or propyl alcohol.
3. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that the step（2）
Chemical vapor deposition unit selected from hot activation chemical vapor deposition unit, plasma activation chemical vapor deposition unit in
It is a kind of.
4. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that the step（2）
In reaction pressure be 1-2KPa.
5. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that the step（2）
Middle carbon source is benzene or toluene.
6. the preparation method of lithium ion battery negative material according to claim 1, it is characterised in that the step（2）
Middle hydrogen and the air pressure of carbon source ratio are 2：1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186350A (en) * | 1998-01-09 | 1998-07-01 | 浙江大学 | Carbon based composite material for cathode of lithium ion secondary battery and manufacture thereof |
| CN101494286A (en) * | 2007-12-04 | 2009-07-29 | 法拉赛斯能源公司 | Secondary battery material |
| CN101662022A (en) * | 2009-09-24 | 2010-03-03 | 无锡欧力达新能源电力科技有限公司 | Nano coating of negative electrode materials and preparation method of secondary aluminium cell using negative electrode materials |
| CN102893430A (en) * | 2010-08-03 | 2013-01-23 | 日立麦克赛尔能源株式会社 | Negative electrode for non-aqueous secondary battery, and non-aqueous secondary battery |
| CN106025220A (en) * | 2016-06-24 | 2016-10-12 | 中天储能科技有限公司 | Silicon oxide-based silicon-oxygen-carbon composite material and preparation method and application thereof |
-
2017
- 2017-10-12 CN CN201710945811.2A patent/CN107681144A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186350A (en) * | 1998-01-09 | 1998-07-01 | 浙江大学 | Carbon based composite material for cathode of lithium ion secondary battery and manufacture thereof |
| CN101494286A (en) * | 2007-12-04 | 2009-07-29 | 法拉赛斯能源公司 | Secondary battery material |
| CN101662022A (en) * | 2009-09-24 | 2010-03-03 | 无锡欧力达新能源电力科技有限公司 | Nano coating of negative electrode materials and preparation method of secondary aluminium cell using negative electrode materials |
| CN102893430A (en) * | 2010-08-03 | 2013-01-23 | 日立麦克赛尔能源株式会社 | Negative electrode for non-aqueous secondary battery, and non-aqueous secondary battery |
| CN106025220A (en) * | 2016-06-24 | 2016-10-12 | 中天储能科技有限公司 | Silicon oxide-based silicon-oxygen-carbon composite material and preparation method and application thereof |
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Application publication date: 20180209 |
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