CN101521278A - Method for preparing anode material of lithium-ion battery - Google Patents
Method for preparing anode material of lithium-ion battery Download PDFInfo
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- CN101521278A CN101521278A CN200810070689A CN200810070689A CN101521278A CN 101521278 A CN101521278 A CN 101521278A CN 200810070689 A CN200810070689 A CN 200810070689A CN 200810070689 A CN200810070689 A CN 200810070689A CN 101521278 A CN101521278 A CN 101521278A
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- composite material
- mno
- lithium
- ion battery
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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
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Abstract
The invention discloses a method for preparing anode composite material of a lithium-ion battery, comprising the following steps of preparing delta-MnO2 by adopting a high-temperature decomposition method; preparing composite material delta-MnO2-X by adopting an ion injection method, wherein X is a transition metal element, and injecting transition metal ions into the prepared delta-MnO2 which takes flake-shaped as matrix; preparing the composite material into an anode sheet of the battery; scraping off the delta-MnO2-X formed on the surface layer for being used as anode active material and proportionally mixed with other substances; and preparing the anode sheet of the lithium-ion battery after the steps of film coating, drying, tabletting, parching, weighing and the like. As the ion injection technology is adopted, a certain number of transition metal ions are injected into the surface layer of the laminated MnO2, so as to modify the laminated MnO2, strengthen the electrochemical intercalation/deintercalation capability of the lithium ions to the material, and increase the discharge specific capacity of the laminated MnO2. The prepared lithium-ion battery has the advantages of low cost, good performance and environmental protection.
Description
Technical field
The present invention relates to technical field of lithium ion, relate in particular to a kind of utilization ion implantation technique and prepare δ-MnO
2The technical field of-Ti anode composite material of lithium ion battery.
Background technology
Lithium ion battery also is secondary lithium battery, and the quality of its positive electrode is one of key factor of restriction lithium ion battery development, and existing anode material for lithium-ion batteries is with LiCoO
2Be main, although LiCoO
2Have than excellent electrochemical properties, but cobalt resource shortage and costing an arm and a leg, pollutes greatlyyer, so people are seeking the cobalt system substitute of positive electrode in addition always.Mn oxide because of its aboundresources, cheap, the feature of environmental protection is good etc., and advantage receives much concern, wherein, layered manganese oxide (δ-MnO
2) with its good layer structure, the insertion reaction of deviating from that helps lithium ion, show discharge performance preferably, but its conductance is low, make the performance of material under the heavy-current discharge condition not good, discharge capacity is compared with its theoretical boundary (308mAh/g), also has sizable gap, in addition in charge and discharge process because problem such as the charge-discharge performance that factor such as Jahn-Teller effect causes is relatively poor has also limited the practical application of layered manganese oxide as anode material for lithium-ion batteries.
Ion implantation technique is a kind of material surface modifying technology, is the field that has vitality in the material science, and this method has three big characteristics: 1. can different metal ion injection material top layers be formed different composite materials by producer's needs; 2. ion can cause changes of microstructure after injecting the top layer, but experiment confirm its to MnO
2Layer structure do not have destructiveness; 3. the injection of ion is not subjected to the restriction of phase rule and chemical balance, and the injection rate of ion is injected the degree of depth, and available implanter is accurately controlled, and its method repeatability and stability are all good, can carry out industrial mass and make.About the application of ion implantation technique, existing many bibliographical informations, but do not see to have this technology is used for δ-MnO
2The material structure modification is to optimize the relevant report of anode material for lithium-ion batteries chemical property.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of employing ion implantation technique, inject a certain amount of transition metal ions in the table of layered manganese oxide, construct δ-MnO
2-X composite material, wherein X is a transition metal, has improved δ-MnO
2Surface structure, strengthen lithium ion and embed/deviate from ability in the electrochemistry of this material, improve stratiform MnO
2Specific discharge capacity.After making the layered manganese oxide modification, become anode material for lithium-ion batteries.
The present invention overcomes the above problems the technical scheme that is adopted to be: a kind of anode composite material of lithium ion battery preparation method comprises the steps:
(1) adopt high-temperature decomposition to prepare δ-MnO
2Heating rate is 50～60 ℃/h, keeps about constant temperature 10h when being warming up to 800～900 ℃, and then reduces to room temperature by same speed;
(2) adopt ion implantation to prepare composite material δ-MnO
2-X; Wherein X is a transition metal, i.e. any element in IB～VIIB subgroup and the VIII family is with the δ-MnO that makes
2Sieve behind elder generation's porphyrize, compacting is a matrix with the sheet in flakes again, uses implanter implanting transition metal ion then; Its ion implantation energy is 60kV, implantation dosage 5 * 10
17Ion/cm
2, transition metal ions purity〉and 99.9%, degree of depth 250nm is injected in the machine control, injects about 150 ℃ of sample target chamber temperature, injection length 2h;
(3) composite material is made battery anode slice; Scrape δ-Mn O that the top layer forms gently with sharp knife edges
2-X, levigate Powdered composite material; Respectively with δ-MnO
2-X do positive electrode active materials and and acetylene black, Kynoar (PVDF) and solvent N-methyl pyrrolidone (NMP) mix by the 85:10:5:100 mass ratio, on the round aluminium flake of diameter, film, drying, compressing tablet, dry and step such as weigh is made based lithium-ion battery positive plate for 1.5cm roughly.
Described transition metal can be a titanium.
Described employing high-temperature decomposition prepares δ-MnO
2Step can be carried out in Muffle furnace.
The beneficial effects of the utility model are: owing to adopt ion implantation technique, inject a certain amount of transition metal ions in the table of layered manganese oxide, construct δ-MnO
2-X composite material, wherein X is a transition metal, has improved δ-MnO
2Surface structure, make the layered manganese oxide modification, strengthen lithium ion and embed/deviate from ability in the electrochemistry of this material, improve stratiform MnO
2Specific discharge capacity, the lithium ion battery of making has that cost is low, performance good, the advantage of environmental protection.
The present invention is further detailed explanation below by embodiment
Embodiment
First kind of embodiment of the present invention, a kind of anode composite material of lithium ion battery preparation method, the preparation method comprises the steps:
(1) in Muffle furnace, adopt high-temperature decomposition to prepare δ-MnO
2Heating rate is 50 ℃/h, keeps about constant temperature 10h when being warming up to 800 ℃, and then reduces to room temperature by same speed;
(2) adopt ion implantation to prepare composite material δ-MnO
2-Ti; With the δ-MnO that makes
2Sieving behind elder generation's porphyrize, with the tablet press machine compacting in flakes, is matrix with the sheet again, injects titanium ion with the MEVVA implanter then; Its ion implantation energy is 60kV, implantation dosage 5 * 10
17Ion/cm
2, titanium ion purity〉and 99.9%, degree of depth 250nm is injected in the machine control, injects about 150 ℃ of sample target chamber temperature, injection length 2h;
(3) composite material is made battery anode slice; Scrape δ-MnO that the top layer forms gently with sharp knife edges
2-Ti, levigate Powdered composite material; Respectively with δ-MnO
2-Ti do positive electrode active materials and and acetylene black, Kynoar (PVDF) and solvent N-methyl pyrrolidone (NMP) mix by the 85:10:5:100 mass ratio, on the round aluminium flake of diameter, film, drying, compressing tablet, dry and step such as weigh is made based lithium-ion battery positive plate for 1.5cm roughly.
Second kind of embodiment of the present invention, a kind of anode composite material of lithium ion battery preparation method, the preparation method comprises the steps:
(1) in Muffle furnace, adopt high-temperature decomposition to prepare δ-MnO
2Heating rate is 55 ℃/h, keeps about constant temperature 10h when being warming up to 850 ℃, and then reduces to room temperature by same speed;
All the other steps and first kind of embodiment are identical, repeat no more.
The third embodiment of the present invention, a kind of anode composite material of lithium ion battery preparation method, the preparation method comprises the steps:
(1) in Muffle furnace, adopt high-temperature decomposition to prepare δ-MnO
2Heating rate is 60 ℃/h, keeps about constant temperature 10h when being warming up to 900 ℃, and then reduces to room temperature by same speed;
All the other steps and first kind of embodiment are identical, repeat no more.
More than among three kinds of embodiment, if will be with other kind transition metal, i.e. any element in IB～VIIB subgroup and the VIII family, step and process conditions are identical, difference only is the Ti element changed into injects other any transition metal.
The battery anode slice made from above-mentioned preparation method carries out the preparation of lithium ion battery can be in being filled with the glove box of argon atmospher, do with electrode to be measured anodal, 1mol/L LiClO
4PC/DME (volume ratio is 1:1) mixed liquor be electrolyte, metal lithium sheet is a negative pole, is assembled into lithium ion battery.
To carry out charge-discharge test to the lithium ion battery that is assembled into, the lithium ion battery that is assembled into can be left standstill 12h after, on charging-discharge tester system, carry out charge-discharge test.In 2～4.0V scope, carry out the charge and discharge cycles test with 0.2C (36mA/g) current ratio condition.
Claims (3)
1, a kind of anode composite material of lithium ion battery preparation method, it is characterized in that: the preparation method comprises the steps:
(1) adopt high-temperature decomposition to prepare δ-MnO
2Heating rate is 50～60 ℃/h, keeps about constant temperature 10h when being warming up to 800～900 ℃, and then reduces to room temperature by same speed;
(2) adopt ion implantation to prepare composite material δ-MnO
2-X; Wherein X is a transition metal, i.e. any element in IB～VIIB subgroup and the VIII family is with the δ-MnO that makes
2Sieve behind elder generation's porphyrize, compacting is a matrix with the sheet in flakes again, uses implanter implanting transition metal ion then; Its ion implantation energy is 60kV, implantation dosage 5 * 10
17Ion/cm
2, transition metal ions purity〉and 99.9%, degree of depth 250nm is injected in the machine control, injection sample target chamber temperature=150 ℃, injection length 2h;
(3) composite material is made battery anode slice; Scrape δ-MnO that the top layer forms gently with sharp knife edges
2-X, levigate Powdered composite material; Respectively with δ-MnO
2-X do positive electrode active materials and and acetylene black, Kynoar and solvent N-methyl pyrrolidone mix by the 85:10:5:100 mass ratio, on the round aluminium flake of diameter, film, drying, compressing tablet, dry and step such as weigh is made based lithium-ion battery positive plate for 1.5cm roughly.
2, a kind of anode composite material of lithium ion battery preparation method according to claim 1, it is characterized in that: described transition metal is a titanium.
3, a kind of anode composite material of lithium ion battery preparation method according to claim 1 and 2, it is characterized in that: described employing high-temperature decomposition prepares δ-MnO
2Step is carried out in Muffle furnace.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810070689A CN101521278A (en) | 2008-02-27 | 2008-02-27 | Method for preparing anode material of lithium-ion battery |
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|---|---|---|---|
| CN200810070689A CN101521278A (en) | 2008-02-27 | 2008-02-27 | Method for preparing anode material of lithium-ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477475A (en) * | 2011-04-19 | 2013-12-25 | 丰田自动车株式会社 | Lithium secondary battery |
| CN110102287A (en) * | 2018-02-01 | 2019-08-09 | 北京化工大学 | A kind of metal-doped modified layered δ-MnO2And its it prepares and applies |
| CN114927632A (en) * | 2022-05-16 | 2022-08-19 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
-
2008
- 2008-02-27 CN CN200810070689A patent/CN101521278A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477475A (en) * | 2011-04-19 | 2013-12-25 | 丰田自动车株式会社 | Lithium secondary battery |
| US20140030598A1 (en) * | 2011-04-19 | 2014-01-30 | Mitsuru Sakano | Lithium secondary battery |
| CN103477475B (en) * | 2011-04-19 | 2015-07-29 | 丰田自动车株式会社 | Lithium secondary battery |
| US9553306B2 (en) | 2011-04-19 | 2017-01-24 | Toyota Jidosha Kabushiki Kaisha | Lithium secondary battery |
| CN110102287A (en) * | 2018-02-01 | 2019-08-09 | 北京化工大学 | A kind of metal-doped modified layered δ-MnO2And its it prepares and applies |
| CN110102287B (en) * | 2018-02-01 | 2021-06-22 | 北京化工大学 | Metal-doped modified layered delta-MnO2And their preparation and use |
| CN114927632A (en) * | 2022-05-16 | 2022-08-19 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
| CN114927632B (en) * | 2022-05-16 | 2024-01-26 | 湘潭大学 | Modified zinc metal sheet and preparation method and application thereof |
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Application publication date: 20090902 |