CN100386377C - Low temperature thermolytic polyacrylonitrile composite tin base cathode material preparation method - Google Patents
Low temperature thermolytic polyacrylonitrile composite tin base cathode material preparation method Download PDFInfo
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- CN100386377C CN100386377C CNB200610012168XA CN200610012168A CN100386377C CN 100386377 C CN100386377 C CN 100386377C CN B200610012168X A CNB200610012168X A CN B200610012168XA CN 200610012168 A CN200610012168 A CN 200610012168A CN 100386377 C CN100386377 C CN 100386377C
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- polyacrylonitrile
- tin
- low temperature
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000010406 cathode material Substances 0.000 title claims description 8
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 13
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 13
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- -1 methane amide Chemical class 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 238000000197 pyrolysis Methods 0.000 abstract description 9
- 239000007773 negative electrode material Substances 0.000 abstract 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- JJNZXLAFIPKXIG-UHFFFAOYSA-N 2-Chlorobenzylidenemalononitrile Chemical compound ClC1=CC=CC=C1C=C(C#N)C#N JJNZXLAFIPKXIG-UHFFFAOYSA-N 0.000 description 2
- 229910006913 SnSb Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention relates to a preparing method for a polyacryl-nitrile tin-based composite negative electrode material by low temperature pyrogenation, which belongs to the field of the preparation technique for new materials, particularly to a preparation technique of negative electrode materials for lithium ion batteries. The present invention is characterized in that the polyacrylonitrile and tin protochloride are firstly uniformly mixed through a solvent; after the solvent is distilled to dryness and the mixture is baked, the mixture is processed by low-temperature pyrolysis at the temperature of 250 DEG C to 450 DEG C so as to obtain the tin-based composite negative electrode material. The composite material prepared by adopting the method has the advantages of high capacity, excellent cycle performance, low material cost of the preparation method, simplified technical process and great application value.
Description
Technical field
The preparation method of low temperature thermolytic polyacrylonitrile composite tin base cathode material belongs to technical field of new material preparation, particularly the technology of preparing of lithium ion battery negative material.
Background technology
Lithium ion battery is the novel high-energy secondary cell that twentieth century begins practicability the nineties, have that voltage height, energy density are big, outstanding advantages such as good cycle, self-discharge are little, memory-less effect, be widely used in field of portable devices such as mobile telephone, notebook computer, digital product, power tool.Lithium ion battery is as the applications well prospect that electrical source of power showed of electromobile and hybrid vehicle and in the huge applications potentiality of numerous areas such as military equipment, aerospace.
Since eighties of last century lithium ion battery at the beginning of the nineties comes out, with the graphitized carbon material is that negative pole, cobalt acid lithium material are that anodal lithium-ion electric pool technology has obtained huge development, is example with notebook computer with 18650 type batteries, about its specific energy was doubled in 10 years.At present, commercial lithium ion battery still mainly is that negative pole, cobalt acid lithium material are anodal with the graphitized carbon material.Along with developing rapidly of information technology, be the continuous miniaturization of handheld device, the intellectuality of representative with mobile telephone, notebook computer etc., require its power supply high-energy-densityization more.In addition, field such as electromobile requires motive-power battery must have higher energy density, lower cost and better security.The performance of commodity lithium ion battery more and more can not satisfy the requirement of above-mentioned development, and wherein negative material is one of important restraining factors.
The subject matter that graphite cathode material exists is: (1) electrographite needs to make through the high temperature graphitization processing at 1900 ℃～2800 ℃, and temperature is too high; (2) theoretical specific capacity is 372mAh/g, and is lower; (3) weak structure can cause very limited stability, and is also extremely sensitive to electrolytic solution.For overcoming these shortcomings, people are devoted to research and develop new negative material always when graphite material is constantly carried out modification.At present, the negative material of lithium ion battery also has amorphous carbon material, silica-base material, tin-based material, other negative material such as novel alloy except that graphite material.The reversible capacity of wherein non-carbon class material is more much higher than the classical capacity 372mAh/g of graphite, can form Li such as the Li-Sn binary system
4.4The alloy of Sn, theoretical capacity is up to 994mAh/g.But this metalloid alloy negative material volume change in the removal lithium embedded process is very big, and its structural stability is very poor, thereby causes alloy pulverization to lose efficacy, and cycle performance is relatively poor.In recent years, people by with metal and other materials particularly carbon material carry out compoundly, obtained the matrix material of capacity height, good cycle.This has benefited from the heavy body of alloy material on the one hand, also has benefited from stability of structure in the carbon material working cycle on the other hand.For example H.Li etc. (sees Chem.Mater. (materials chemistry) 2002,14:103) prepared the SnSb/HCS matrix material, wherein HCS is that diameter is the nanoporous carbosphere of 5-20 μ m, in the ball is but the undefined structure of graphite linings composition, and the aperture that wherein distributing is the nanoporous of 0.5-3nm.With HCS is skeleton, with nanometer SnSb alloying pellet equably pinning in its surface, the rare fusion of Nanoalloy particle is reunited in charge and discharge process like this, thereby has excellent cycle performance, 35 times the round-robin reversible capacity is stabilized in about 500mAh/g.
The present invention is a raw material with polyacrylonitrile and tin protochloride, and by the dissolving uniform mixing, the method for low temperature thermolytic polyacrylonitrile prepares the tinbase cathode composite materials, provides a kind of method simply direct, with low cost for preparing the tinbase cathode composite materials.
Summary of the invention
The present invention polyacrylonitrile and tin protochloride uniform mixing, after solvent evaporated and the oven dry, carries out low temperature pyrogenation by solvent under 250～450 ℃, preparation tinbase cathode composite materials.Tin protochloride itself does not have electroconductibility, and the product after the polyacrylonitrile pyrolysis has electroconductibility, therefore will just have electroconductibility behind the two uniform mixing; Itself has lithium storage content tin, and the two just mixes and can use as the negative material of lithium ion battery, and the cycle performance of this product is good.
The tinbase cathode composite materials preparation method that the present invention proposes.It is characterized in that the preparation method of low temperature thermolytic polyacrylonitrile composite tin base cathode material is characterized in that, contain following steps successively:
1) polyacrylonitrile and tin protochloride are dissolved in the volatilizable solvent that can dissolve described polyacrylonitrile and tin protochloride, wherein the mass ratio of polyacrylonitrile and tin protochloride is 1: 2～1: 6;
2) with the 1st) the solvent evaporate to dryness of the mixture solution that obtains of step, and mixture further dried;
3) with the 2nd) mixture that obtains of step heats under protection of inert gas, obtains the tinbase cathode composite materials, and wherein Heating temperature is 250 ℃～450 ℃, and soaking time was greater than 2 hours.
Described volatilizable solvent is dimethylin methane amide, methyl-sulphoxide or propane dinitrile.
Described rare gas element is argon gas or nitrogen.
Evidence: this matrix material have capacity and a cycle performance preferably, the cost of material is low for its preparation method, technical process is simple, has very big using value, reached its intended purposes.
Description of drawings
Fig. 1 is PAN and SnCl
22H
2The mass ratio of O is 1: 4 o'clock, the capacity cycle diagram of the material for preparing during to lithium anode.
Embodiment
The core of the technical program is tin protochloride and polyacrylonitrile mixed dissolution, solvent evaporated then, with the material that obtains mixing, then by pyrolysis, make polyacrylonitrile have the conductive polymer sub-feature, thus processability good contain tin chloride and the even compound tinbase of thermolytic polyacrylonitrile product cathode composite materials.Use solvent to be dimethylin methane amide, methyl-sulphoxide or propane dinitrile, consider that mainly this solvent can dissolve polyacrylonitrile and tin protochloride simultaneously, and take into account the cost of considering this solvent simultaneously.During evaporate to dryness, solvent can reclaim, and reuses.
The objective of the invention is to be achieved through the following technical solutions:
Take by weighing a certain amount of polyacrylonitrile and tin protochloride, be dissolved in the certain amount of solvent.Solvent evaporated, low temperature pyrogenation just can obtain the tinbase cathode composite materials.This material has higher capacity and excellent cycle performance.
Introduce embodiments of the invention below:
Embodiment one. get 1 gram PAN and 4 gram SnCl
22H
2O is dissolved in 50 milliliters of dimethyl formamides stirring and dissolving, and (amount of solvent is able to PAN and SnCl
22H
2O fully dissolves just passable, and solvent need be removed, and is few more economical more.Being that pyrolysis time is long very little, is to remove the time length of desolvating too much).Then in 60 ℃ of heating down, solvent evaporated.In the gas shield stove, in 450 ℃ of pyrolysis 2 hours, can obtain the tinbase cathode composite materials under the nitrogen protection to dried mixture.Fig. 1 is the capacity cycle diagram of this material during to lithium anode, and testing method is the common testing method of known lithium ion battery negative material.This material has the circulation volume of 500mAh/g after tested.
Embodiment two. get 1 gram PAN and 3 gram SnCl
22H
2O is dissolved in 100 milliliters of methyl-sulphoxides, stirring and dissolving.Then in 80 ℃ of heating down, solvent evaporated.Dried mixture under nitrogen protection in 300 ℃ of pyrolysis 5 hours, can obtain the tinbase cathode composite materials.This material has the circulation volume of 372mAh/g after tested.
Embodiment three. get 1 gram PAN and 2 gram SnCl
22H
2O is dissolved in 100 milliliters of propane dinitrile, stirring and dissolving.Then in 60 ℃ of heating down, solvent evaporated.Dried mixture under nitrogen protection in 250 ℃ of pyrolysis 30 hours (when greater than 30 constantly slight, the not too big variation of the performance of product), can obtain the tinbase cathode composite materials.This material has the circulation volume of 310mAh/g after tested.
Embodiment four. get 1 gram PAN and 5 gram SnCl
2.2H
2O is dissolved in 50 milliliters of dimethyl formamides, stirring and dissolving.Then in 120 ℃ of heating down, solvent evaporated.Dried mixture under nitrogen protection in 300 ℃ of pyrolysis 5 hours, can obtain the tinbase cathode composite materials.This material has the circulation volume of 570mAh/g after tested.
Embodiment five. get 1 gram PAN and 6 gram SnCl
2.2H
2O is dissolved in 50 milliliters of dimethyl formamides, stirring and dissolving.Then in 60 ℃ of heating down, solvent evaporated.Dried mixture under nitrogen protection in 280 ℃ of pyrolysis 10 hours, can obtain the tinbase cathode composite materials.This material has the circulation volume of 610mAh/g after tested.
Claims (3)
1. the preparation method of low temperature thermolytic polyacrylonitrile composite tin base cathode material is characterized in that, contains following steps successively:
1) polyacrylonitrile and tin protochloride are dissolved in the volatilizable solvent that can dissolve described polyacrylonitrile and tin protochloride, wherein the mass ratio of polyacrylonitrile and tin protochloride is 1: 2～1: 6;
2) with the 1st) the solvent evaporate to dryness of the mixture solution that obtains of step, and mixture further dried;
3) with the 2nd) mixture that obtains of step heats under protection of inert gas, obtains the tinbase cathode composite materials, and wherein Heating temperature is 250 ℃～450 ℃, and soaking time was greater than 2 hours.
2. the preparation method of low temperature thermolytic polyacrylonitrile composite tin base cathode material as claimed in claim 1 is characterized in that, described volatilizable solvent is dimethylin methane amide, methyl-sulphoxide or propane dinitrile.
3. the preparation method of low temperature thermolytic polyacrylonitrile composite tin base cathode material as claimed in claim 1 is characterized in that, described rare gas element is argon gas or nitrogen.
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| CNB200610012168XA CN100386377C (en) | 2006-06-09 | 2006-06-09 | Low temperature thermolytic polyacrylonitrile composite tin base cathode material preparation method |
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| CNB200610012168XA CN100386377C (en) | 2006-06-09 | 2006-06-09 | Low temperature thermolytic polyacrylonitrile composite tin base cathode material preparation method |
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| CN100386377C true CN100386377C (en) | 2008-05-07 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385464A (en) * | 2001-05-11 | 2002-12-18 | 崔蔚 | Organic compound material containing inorganic nano material, its preparation method and use |
| US20040081892A1 (en) * | 2002-10-24 | 2004-04-29 | Haruo Sawa | Solid electrolyte with high ion conductivity and electrochemical system using the solid electrolyte |
| CN1740216A (en) * | 2005-09-27 | 2006-03-01 | 北京理工大学 | Polyurethane foam metallizing treatment process |
| JP2006073356A (en) * | 2004-09-02 | 2006-03-16 | Nitto Denko Corp | Ion-conductive solid electrolyte |
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2006
- 2006-06-09 CN CNB200610012168XA patent/CN100386377C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385464A (en) * | 2001-05-11 | 2002-12-18 | 崔蔚 | Organic compound material containing inorganic nano material, its preparation method and use |
| US20040081892A1 (en) * | 2002-10-24 | 2004-04-29 | Haruo Sawa | Solid electrolyte with high ion conductivity and electrochemical system using the solid electrolyte |
| JP2006073356A (en) * | 2004-09-02 | 2006-03-16 | Nitto Denko Corp | Ion-conductive solid electrolyte |
| CN1740216A (en) * | 2005-09-27 | 2006-03-01 | 北京理工大学 | Polyurethane foam metallizing treatment process |
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