CN103956496A - Lithium ion battery negative active material and preparation method thereof - Google Patents
Lithium ion battery negative active material and preparation method thereof Download PDFInfo
- Publication number
- CN103956496A CN103956496A CN201410176900.1A CN201410176900A CN103956496A CN 103956496 A CN103956496 A CN 103956496A CN 201410176900 A CN201410176900 A CN 201410176900A CN 103956496 A CN103956496 A CN 103956496A
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- lithium ion
- ion battery
- active material
- tin
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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
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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
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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
- H01M4/364—Composites as mixtures
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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 lithium ion battery negative material and a preparation method thereof. An outer layer of the negative material is made of a soft carbon material, and an inner core covered with the outer layer is made from a compound of hard carbon and nanometer silicon or/and tin; the mass ratio of the soft carbon material at the outer layer to the inner core compound covered with the outer layer is 18%-20%. The preparation method comprises the steps of feeding a certain amount of nano amorphous silicon or/and tin into an organic solution of macromolecular organic polymer, carrying out ultrasonic shaking and drying, then carrying out pyrolysis, and mixing the product with the soft carbon material by ball milling to obtain the lithium ion battery negative active material. According to the lithium ion battery negative material and the preparation method thereof, hard carbon is compounded with silicon/tin, so that the volume effect of silicon/tin is inhibited, the cycle performance of the material is improved while the volume is increased, and the material is stable in structure by virtue of compounding.
Description
Technical field
The present invention relates to a kind of battery active material and preparation method, particularly a kind of lithium ion battery anode active material and preparation method.
Background technology
Lithium ion battery generally adopts at present using carbon materials that native graphite, soft carbon be representative as negative material, and its cycle performance is better, but capacity low (theoretical capacity is only 372mAh/g), doubly forthright poor can not meet the needs of people to lithium battery applications.
In recent years, research finds that some inorganic material have the characteristic of high power capacity, for example the specific capacity of nano-silicon is 990mAh/g up to the specific capacity of 4000mAh/g, tin, therefore silicon, tin are desirable substitute products, but all there is serious bulk effect in silicon, tin negative pole material in the de-embedding process of lithium, therefore cycle performance is poor, is seriously restricting the application of silicon, tin base cathode material.Preparing silicon, the tin negative pole material with long cycle performance becomes a large problem of negative material research
The carbon element negative material that another kind receives much concern is hard carbon, is the RESEARCH OF PYROCARBON of high molecular polymer, and it is also difficult to graphitization above at 2500 ℃.Hard carbon material all has higher reversible specific capacity, be generally (500 ~ 700mAh/g), common hard carbon has resin carbon (as phenolic resins, epoxy resin and poly furfuryl alcohol PFA-C etc.), organic polymer RESEARCH OF PYROCARBON (as PFA, PVC, PVDF and PAN etc.) and carbon black (acetylene black) etc., but hard carbon material exists electrode potential too high, current potential lags behind, the large shortcoming of irreversible capacity, makes it can't obtain business-like application first.
Summary of the invention
The present invention aims to provide a kind of good cycle, capacity is high, commercial applications has good prospects lithium ion battery negative material and preparation method.The present invention realizes by following scheme:
A lithium ion battery anode active material, skin is soft material with carbon element, coated kernel is that hard carbon and nano-silicon are or/and the compound of tin; Described hard carbon is the material with carbon element of high molecular polymer after pyrolysis, as the RESEARCH OF PYROCARBON such as PFA, PVC, PVDF and PAN and carbon black (acetylene black) etc., described soft carbon is one or both in needle coke or pitch coke, and outer soft material with carbon element is (18～20) with coated kernel compound quality ratio: 100.
Through experiment, find, nano-silicon in kernel is or/and the quality of tin accounts for 2%～4% of active material gross mass, and material combination property is better.
The preparation method of lithium ion battery anode active material, by a certain amount of nanometer amorphous silicon or/and tin join in the organic solution of macromolecule organic polymer, through ultrasonic concussion---after being dried, Pintsch process under 600-800 ℃ of condition, adopt ball-milling method to mix with a certain amount of soft material with carbon element the compound obtaining again afterwards, make lithium ion battery anode active material.Hard carbon is the material with carbon element of high molecular polymer after pyrolysis, and as the RESEARCH OF PYROCARBON such as PFA, PVC, PVDF and PAN and carbon black (acetylene black) etc., soft carbon is one or both in needle coke or pitch coke.For preparing preferably material of combination property, nanometer amorphous silicon is or/and the mass ratio of tin and macromolecule organic polymer is (3～5): 100 for excellent.
The compound quality obtaining after soft carbon and Pintsch process is than being (18～20): 100.
Compared with prior art, the invention has the advantages that: due to compound by hard carbon and silicon/tin of the present invention, thereby suppressed the bulk effect of silicon/tin, when improving capacity, improved the cycle performance of material, this compound Stability Analysis of Structures that also can make material.
Embodiment
embodiment 1
Prepare according to the following steps a kind of lithium ion battery anode active material:
The first step: nanometer amorphous silicon is joined in the solution of the macromolecule organic polymer PVDF being dissolved in ethanol, wherein the addition of amorphous silicon is 3% of PVDF quality;
Second step: the muddy organic liquor that upper step obtains is through ultrasonic concussion---after being dried, Pintsch process under 750 ℃ of conditions, obtains embedding silicon hard carbon compound;
The 3rd step: the embedding silicon hard carbon compound again second step being obtained afterwards adopts ball-milling method to mix with needle coke, and wherein the mass ratio of needle coke and embedding silicon hard carbon compound is 20%, makes lithium ion battery anode active material.
embodiment 2
The lithium ion battery anode active material that embodiment 1 prepares, skin is soft carbon needle coke, coated kernel is the compound of hard carbon and nano-silicon; After measured, in active material, nano-silicon accounts for 2.5% of active material gross mass.
Adopt respectively the material of the present embodiment and commercially available for lithium ion battery, Delanium (comparative example) is as the negative active core-shell material of 18650 lithium ion batteries, all the other conditions are all identical, and test result is as following table:
Test result shows: the material of the embodiment of the present invention is having a distinct increment aspect capacity and high rate performance.
embodiment 3
Preparation method is basic identical with embodiment 1, but adopts amorphous nanometer tin to join in the acetone soln of PVC, and wherein the addition of amorphous tin is 5% of PVC quality.
The material structure that adopts this method to make is basic identical with embodiment 2, but in active material, nanometer tin accounts for 4% of gross mass.
Above-mentioned material is made the negative pole of 18650 batteries, and after tested, the gram volume of battery can reach 390mAh/g, and first effect reaches 96%, and doubly forthright is 35C, and capacity and high rate performance are good.
Claims (5)
1. a lithium ion battery anode active material, is characterized in that: outer is soft material with carbon element, and coated kernel is that hard carbon and nano-silicon are or/and the compound of tin; Described hard carbon is the material with carbon element of high molecular polymer after pyrolysis, and described soft carbon is one or both in needle coke or pitch coke, outer soft material with carbon element with coated kernel compound quality than 18%～20%.
2. lithium ion battery anode active material as claimed in claim 1, is characterized in that: nano-silicon in described kernel is or/and the quality of tin accounts for 2%～4% of active material gross mass.
3. the preparation method of a lithium ion battery anode active material as claimed in claim 1 or 2, it is characterized in that: by a certain amount of nanometer amorphous silicon or/and tin join in the organic solution of macromolecule organic polymer, through ultrasonic concussion---after being dried, Pintsch process under 600～800 ℃ of conditions, adopt ball-milling method to mix with a certain amount of soft material with carbon element the compound obtaining again afterwards, make lithium ion battery anode active material.
4. the preparation method of lithium ion battery anode active material as claimed in claim 3, is characterized in that: described nanometer amorphous silicon is or/and the mass ratio of tin and described macromolecule organic polymer is (3～5): 100.
5. the preparation method of the lithium ion battery anode active material as described in claim 3 or 4, is characterized in that: when described ball-milling method mixes, the compound quality obtaining after the soft carbon of use and described Pintsch process is than being (18～20): 100.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410176900.1A CN103956496A (en) | 2014-04-29 | 2014-04-29 | Lithium ion battery negative active material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410176900.1A CN103956496A (en) | 2014-04-29 | 2014-04-29 | Lithium ion battery negative active material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104882590A (en) * | 2015-06-17 | 2015-09-02 | 田东 | Preparation method of carbon/ graphite/ silicon composited anode material |
| CN104953100A (en) * | 2015-06-17 | 2015-09-30 | 田东 | Preparation method of carbon/graphite/tin composite anode material |
| CN104966828A (en) * | 2015-08-07 | 2015-10-07 | 田东 | Preparation method of high-capacity lithium battery negative electrode material |
| CN105047891A (en) * | 2015-07-10 | 2015-11-11 | 田东 | Preparation method of graphite tin-based composite anode material |
| CN107681125A (en) * | 2016-08-02 | 2018-02-09 | 微宏动力***（湖州）有限公司 | A kind of cathode material of lithium ion battery, its preparation method and lithium rechargeable battery |
| CN109950548A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院物理研究所 | A kind of carbon composite and its preparation method and application for secondary cell |
| CN114864909A (en) * | 2022-06-13 | 2022-08-05 | 珠海冠宇电池股份有限公司 | Negative electrode material, negative plate comprising negative electrode material and battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101887966A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon cathode material of lithium ion battery and preparation method thereof |
| CN103326023A (en) * | 2013-06-07 | 2013-09-25 | 浙江瓦力新能源科技有限公司 | High-performance lithium ion battery silicon-carbon cathode material and preparation method thereof |
-
2014
- 2014-04-29 CN CN201410176900.1A patent/CN103956496A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101887966A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon cathode material of lithium ion battery and preparation method thereof |
| CN103326023A (en) * | 2013-06-07 | 2013-09-25 | 浙江瓦力新能源科技有限公司 | High-performance lithium ion battery silicon-carbon cathode material and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104882590A (en) * | 2015-06-17 | 2015-09-02 | 田东 | Preparation method of carbon/ graphite/ silicon composited anode material |
| CN104953100A (en) * | 2015-06-17 | 2015-09-30 | 田东 | Preparation method of carbon/graphite/tin composite anode material |
| CN105047891A (en) * | 2015-07-10 | 2015-11-11 | 田东 | Preparation method of graphite tin-based composite anode material |
| WO2017008606A1 (en) * | 2015-07-10 | 2017-01-19 | 田东 | Method for fabricating graphite tin-based composite negative-electrode material |
| CN104966828A (en) * | 2015-08-07 | 2015-10-07 | 田东 | Preparation method of high-capacity lithium battery negative electrode material |
| CN107681125A (en) * | 2016-08-02 | 2018-02-09 | 微宏动力***（湖州）有限公司 | A kind of cathode material of lithium ion battery, its preparation method and lithium rechargeable battery |
| CN107681125B (en) * | 2016-08-02 | 2021-04-16 | 微宏动力***（湖州）有限公司 | Negative electrode material for lithium ion battery, preparation method of negative electrode material and lithium ion secondary battery |
| CN109950548A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院物理研究所 | A kind of carbon composite and its preparation method and application for secondary cell |
| CN114864909A (en) * | 2022-06-13 | 2022-08-05 | 珠海冠宇电池股份有限公司 | Negative electrode material, negative plate comprising negative electrode material and battery |
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Application publication date: 20140730 |