CN102255079A - Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery - Google Patents
Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery Download PDFInfo
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- CN102255079A CN102255079A CN2011101294954A CN201110129495A CN102255079A CN 102255079 A CN102255079 A CN 102255079A CN 2011101294954 A CN2011101294954 A CN 2011101294954A CN 201110129495 A CN201110129495 A CN 201110129495A CN 102255079 A CN102255079 A CN 102255079A
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- ion battery
- tin
- phenolic resins
- porous polymer
- carbon composite
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 60
- 239000005011 phenolic resin Substances 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 54
- 229920000642 polymer Polymers 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 45
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000002733 tin-carbon composite material Substances 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- 150000001299 aldehydes Chemical class 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000005255 carburizing Methods 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000011363 dried mixture Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 235000014121 butter Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000011135 tin Substances 0.000 description 26
- 229910052718 tin Inorganic materials 0.000 description 26
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- -1 ethyl carbonate ester Chemical class 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004227 thermal cracking 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
Abstract
The invention provides a stannum-carbon composite material used for lithium ion battery cathodes and a preparation method thereof, and provides a lithium ion battery assembled with the stannum-carbon composite material prepared by the method as an electrode. According to the invention, phenol monomers and aldehyde monomers are used to prepare porous high molecular phenolic resins with high pore volume and high specific surface; on the basis of the porous high molecular phenolic resins, the stannum-carbon composite material with a small particle size, high bonding strength, high specific capacity and stable electrochemical performance is prepared. According to an optimal embodiment in the invention, the initial discharge specific capacity of the cathode material can reach 605 mAh/g and has a specific capacity of 453 mAh/g after 20 cycles.
Description
Technical field
The invention belongs to battery manufacturing technology field, be specifically related to a kind of used as negative electrode of Li-ion battery tin carbon composite and preparation method thereof and lithium ion battery.
Background technology
At present, produce the lithium ion battery that uses and mainly adopt graphitized carbon to be negative material, but the lithium storage content of graphite type material is not high.With regard to the graphite-based negative material, its bigger layer structure space has also determined the characteristic of the low theoretical specific capacity (about 372mAh/g) of this material both for the storage of lithium provides the place.Therefore, the high power capacity of development of new and high magnification negative material have very high research and value.Negative material is discovered as tin, silicon, aluminium, antimony etc. can have the theoretical capacity that is far longer than graphite with the metal or alloy material that lithium forms alloy, has caused the extensive concern of battery material circle.
Tin base cathode material is owing to have very high theoretical gram volume (theoretical specific capacity is 990mAh/g), and low embedding lithium current potential has higher stability and gets most of the attention than other metal_based materials.But tin-based material is the same with other metal_based materials, in the process of removal lithium embedded, exists serious bulk effect, the powder of detached that causes material in charge and discharge process, cause the decay of capacity, not only reduced the efficient and the cycle performance of battery, and have serious potential safety hazard.
The effective way that overcomes the problems referred to above is to adopt composite material, and carbon class negative material change in volume in charge and discharge process is less, has excellent cycle performance, so normal the selection and the alloy composition composite material.Studies show that carbon is a kind of good matrix of metal, if can tin carbon is compound then can bring into play separately advantage: metallic tin can provide bigger capacity, and material with carbon element then has good cyclical stability, and two kinds of materials all can store up lithium.Tin and carbon are carried out compoundly for this reason, cushion volumetric expansion violent in the tin alloying process, utilize carbon skeleton to disperse tin particles simultaneously, suppress the reunion of tin particles, improve the cycle performance of material with the little volumetric expansion (9%) of carbon in the removal lithium embedded process.
People such as the bright friend of fiber crops adopt the tin ash-graphite composite material of Preparation by Uniform Precipitation to have the good lithium of embedding first capacity (The Chinese Journal of Nonferrous Metals, Vol.15No.5 (2005): 793-798), but coulombic efficiency is lower first, capacity attenuation is also than comparatively fast, and this method can not well solve the bulk effect of tin-based material in the removal lithium embedded process.This is because compound or pyrocarbon coats and reduces bulk effect and can not fundamentally suppress bulk effect in the charge and discharge process by physics, and after circulation repeatedly, capacity will begin again to decay rapidly.
People such as Wang Yong adopted the original position synthetic technology prepared the nano-particles filled carbon nano-tube of a kind of tin-carbon/nucleocapsid structure the tin carbon composite (Wang Yong, Jiao just, Wu Minghong etc., a kind of in-situ synthetic method for preparing the nano particle complete filling carbon nano-tube composite negative pole material of tin-carbon/nucleocapsid structure, China Patent No.: 200910048318.6).The original position synthetic technology comes from the notion of in-situ crystallization and in-situ polymerization, refers to that wild phase original position in the material preparation process of a kind of cenotype or composite material produces on the spot, but not synthetic before material preparation.Generated in-situ cenotype can be thing phases such as metal, pottery or macromolecule, they can be present in the matrix with microstructural forms such as particle, whisker, brilliant plate or microfibres, and cenotype combines with basal body interface closely, synthesis technique is simple, and advantage causes that the researcher payes attention to the performance impact of material is big etc.The lithium of the embedding first capacity of this material has reached 700mAh/g, and cycle performance increases, but adopts the carbon nanometer tube material complicated process of preparation, and preparation process is difficult to control, and cost is also more expensive, is difficult to reach the practicability requirement.
Phenolic resins has good pyrolysis and carbonation properties, forms the polymerization carbon of high-bond in pyrolysis (500-900 ℃) process.Under optimum condition, the phenolic resins pyrolysis can obtain the above pure carbon output capacity of 50-60%.RESEARCH OF PYROCARBON electric conducting material by the preparation of phenolic resins thermal cracking is very stable in air, and conductivity can arbitrarily be controlled at 10 with the heat treatment temperature difference
-10-10
2In the S/cm scope, specific area can reach 2000m
2More than/the g.In addition, people discover that making electrode with this cracking material can fill lithium to C
2Li state, capacity are that (theory charges to C to graphite electrode
6Li state, theoretical capacity are 372mAh/g) three times, can reach more than the 1000mAh/g, become one of big capacity electrode material of present people research and development.People such as Dong Wensheng adopt the solvent blending method to prepare pink salt and phenolic resins blended liquid; add ammonia aqueous solution again and pink salt is converted into tin oxide obtains block coagulation, under the nitrogen atmosphere protection, prepare tin oxide/carbon composite electrode material (China Patent No.: 101800306A) at last through carbonization.This method is that simple carbon coats tin material, can not alleviate the bulk effect of tin material effectively, is not fine to the cycle performance that improves this type of material therefore, and along with the increase of cycle-index, material property can further cracking.
Summary of the invention
Technical problem to be solved by this invention is at above shortcomings in the prior art, provides that a kind of raw material is cheap and easy to get, specific capacity is high, good cycling stability and little used as negative electrode of Li-ion battery tin carbon composite and this preparation methods and the lithium ion battery of bulk effect.The tin carbon negative pole material function admirable that obtains, simultaneously synthesis technique is simple, and cost is low, be easy to industrialization.
The technical scheme that solution the technology of the present invention problem is adopted is that this used as negative electrode of Li-ion battery tin carbon composite adopts the carbon matrix raw material source of porous polymer phenolic resins as composite cathode material of lithium ion battery, adopt the tin matter raw material source of stanniferous chloride aqueous solution as composite cathode material of lithium ion battery, this porous polymer phenolic resins is placed the stanniferous chloride aqueous solution, utilize the special pore space structure of porous polymer phenolic resins, forming the stannic hydroxide precipitation by the adding ammonia aqueous solution in the stanniferous chloride aqueous solution is filled in the hole, make generation cracking of porous polymer phenolic resins and carburizing reagent through high-temperature roasting at last, the stannic hydroxide reaction is tin oxide, obtain tin carbon in conjunction with tight and finely dispersed used as negative electrode of Li-ion battery tin carbon composite, wherein tin content is 35-70wt%.The cracking of described porous polymer phenolic resins and carburizing reagent are to carry out under the mixed atmosphere of inert atmosphere or reducing gas and inert gas.
Chinese patent application number: 200910174696.9 have introduced a kind of Hydrophilous porous phenolic resin, its structure is made up of micropore and the mesoporous of 2-50nm of 0.4-1nm, this Hydrophilous porous phenolic resin adsorbance is big, is mainly used in precious metal smelting and reclaims field selective absorption precious metal ion.The present invention utilizes the characteristic of the absorption precious metal ion of Hydrophilous porous phenolic resin, uses it for field of batteries and makes used as negative electrode of Li-ion battery tin carbon negative pole material.
Further preferably, described porous polymer phenolic resins contains the mesoporous of the micropore of 0.4-1nm and 2-50nm, pore volume 0.4-2.4cm
3g
-1, specific surface 450-1000m
2g
-1
Further preferably described porous polymer phenolic resins is to be 1 in molar ratio with phenol monomer and aldehyde monomer: 1-1: 5 are dissolved in the solvent, add acid or alkali and make catalyst, through reacting synthesizing porous polymer, its hole comprises the mesoporous formation of micropore and the 2-50nm of 0.4-1nm.
Further preferably described phenol monomer is one or more in phenol, hydroquinones, catechol, the resorcinol.Described aldehyde monomer is one or more in acetaldehyde, formaldehyde and the benzaldehyde.Described solvent is water or ethanol.Described acid is a kind of in hydrochloric acid, sulfuric acid, the nitric acid.Described alkali is a kind of in NaOH, potassium hydroxide, the sodium carbonate.
Preferably, described stanniferous villaumite is at least a in stannous chloride, butter of tin, the stannic chloride pentahydrate, and the concentration of tin is 1-4mol/L in the stanniferous chloride aqueous solution.
Preferably, high-temperature roasting is 600-750 ℃ of following constant temperature calcining 1-10 hour.
The preparation method of used as negative electrode of Li-ion battery tin carbon composite of the present invention, it comprises the following steps:
(1) preparation porous polymer phenolic resins
The raw material of preparation porous polymer resin is phenol monomer and aldehyde monomer, with phenol monomer and aldehyde monomer is 1 in molar ratio: 1-1: 5 are dissolved in the solvent, wherein the concentration of phenol monomer is 0.5-1.5mol/L, the aldehyde monomer is 0.5-2.5mol/L, add acid or alkali and make catalyst, when making catalyst with acid, the concentration of acid is at 0.1-5mol/L; When making catalyst with alkali, the concentration of alkali is at 0.1-2mol/L.Synthetic reaction obtains porous polymer phenolic resins;
Preferably, described phenol monomer is at least a in phenol, hydroquinones, catechol, the resorcinol.
Preferably, described aldehyde monomer is at least a in acetaldehyde, formaldehyde and the benzaldehyde.
Preferably, described solvent is water or ethanol.
Smash to pieces behind the product natural cooling, 80-120 ℃ vacuumize 6-18 hour, vacuum degree is-0.1MPa that it is stand-by to clay into power with mortar.Synthetic porous polymer contains the mesoporous of the micropore of 0.4-1nm and 2-50nm, and pore volume is 0.4-2.4cm
3g
-1, specific surface 450-1000m
2g
-1
(2) chloride solution of configuration stanniferous
Accurately a certain amount of stanniferous villaumite of weighing is dissolved in the deionized water, and the concentration of tin is 1-4mol/L in the solution.
The stanniferous villaumite is at least a in stannous chloride, butter of tin, the stannic chloride pentahydrate.
(3) preparation stanniferous macromolecule resin
The porous polymer phenolic resins that step (1) is made joins in the tin-salt solution of step (2), the mass ratio of porous polymer phenolic resins and pink salt is 1: 1-1: 3, after soaking 3-9 hour, the ammonia aqueous solution that in solution, dropwise adds 15-30wt%, vigorous stirring in adding the process of ammonia aqueous solution, add ammonia aqueous solution amount calculate by the pink salt in whole precipitation solutions and excessive a little.
Above-mentioned gained mixing suspension is filtered, and with the distilled water washing, under the 80-120 ℃ of temperature vacuumize 6-18 hour, vacuum degree was-0.1MPa.
(4) preparation tin carbon composite
With the dried mixture of step (3) under protective atmosphere; heat with 1-10 ℃/min heating rate; in 600-750 ℃ of following constant temperature calcining 1-10 hour; carry out the cracking and the carburizing reagent of porous polymer phenolic resins, obtain the used as negative electrode of Li-ion battery tin carbon composite of stanniferous 35%-70%.
Preferably, synthetic reaction is that temperature is in 30-180 ℃ of scope in the reactor with the reactant sealing insulation in the reactor of packing in the step (1), and temperature retention time is 0.5 hour to 30 days, when temperature surpasses solvent boiling point, feeds with autoclave.
Above-mentioned protective atmosphere is the mist of inert gas or reducing gas and inert gas, and described inert gas is a kind of in argon gas or the nitrogen; Reducing gas is a hydrogen.
The invention has the beneficial effects as follows: technology is simple, and favorable reproducibility is easy to implement, and prepared after tested material specific capacity height reaches as high as 605mAh/g, good cycling stability, and after 20 circulations, capacity is about 453mAh/g, cost is low.
Description of drawings
Fig. 1 is the stereoscan photograph of the prepared porous polymer phenolic resins with special pore structure of the present invention, and wherein a figure is amplified to other stereoscan photograph of um level, and b figure is amplified to other stereoscan photograph of nm level;
Fig. 2 becomes the cycle performance figure under constant current 0.1C behind the button cell for embodiment one prepared material.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing.
Embodiment one
(1) preparation of porous catechol formaldehyde resin
2.20g catechol, 2ml formaldehyde (37wt%) and 5ml concentrated hydrochloric acid are added in the 10ml ethanol together, the mol ratio of phenol monomer and aldehyde monomer is about 1: 1, stirring is dissolved it fully, with the above-mentioned solution 50ml autoclave of packing into, 100 ℃ of insulations 5 hours, synthetic reaction obtained porous polymer catechol formaldehyde resin gel; The gained gel is smashed to pieces, and under 80 ℃ of temperature dry 18 hours, vacuum degree be-0.1MPa, porous catechol formaldehyde resin, gained material usefulness mortar grind into powder is stand-by.
The porous polymer phenolic resins stereoscan photograph of gained such as Fig. 1 a, shown in the 1b, can find out that by Fig. 1 b sample is alveolate texture, the small and dense collection of hole, it is crosslinked thamnastraeoid that the hole is, it is more even to distribute, the size of aperture and hole wall is all at nanoscale, in low multiple picture, can see some independently circular cavities that distributing in the sample, and its inner surface smoother as can be seen, the formation of these pores mainly is because of the neighbour of phenol by hydroxyl, contraposition and aldehyde generation dehydration, each phenol all has four active sites, so each phenol unit can link to each other with four aldehyde unit at most; The cavity that polymer chain surrounded has just constituted the hole in the polymer.Synthetic expanded phenol-formaldehyde resin polymer contains the mesoporous of the micropore of 0.4-1nm and 2-50nm, and pore volume is 2.4cm
3g
-1, specific area is 1040m
2g
-1
(2) configuration of the chloride solution of stanniferous
Configuration 10mL SnCl
45H
2O solution, accurately a certain amount of stanniferous villaumite of weighing is dissolved in the deionized water, and the concentration of tin is 2mol/L in the solution.
(3) preparation of stanniferous macromolecule resin
The porous polymer phenolic resins 7g that step (1) is made joins in the tin-salt solution of step (2) preparation, be that phenolic resins and pink salt mass ratio are 1: 1, soak after 6 hours, in solution, dropwise add the ammonia aqueous solution that 10mL concentration is 20wt%, vigorous stirring in the process that adds ammonia aqueous solution, obtain mixing suspension, the stannic hydroxide precipitation that generates enters in the hole of porous resin, mixing suspension is filtered, and wash with distilled water, vacuumize 18h under 80 ℃ of temperature, vacuum degree is-0.1MPa.
(4) preparation of tin carbon composite
With the dried mixture of step (3) under argon gas atmosphere protection; heat with 1 ℃/min heating rate; in 600 ℃ of following constant temperature calcinings 10 hours, porous polymer phenolic resins is decomposed and carburizing reagent, obtain the lithium ion battery tin carbon negative pole material of stanniferous 37wt% at last.
The lithium ion battery tin carbon negative pole material of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF (Kynoar) respectively at 80: 10: 10, with NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry, evenly be coated on the Copper Foil, 80 ℃ of vacuumize 24 hours, vacuum degree is-0.1MPa to make the Experimental cell pole piece.Be to electrode with the lithium sheet again, electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell, and under the condition of constant current 0.1C, carry out cycle performance and test, this material first discharge specific capacity is 605mAh/g, after 20 circulations, capacity is about 453mAh/g, as shown in Figure 2.
Embodiment two
(1) preparation of porous hydroquinones formaldehyde resin
3.30g hydroquinones, 12ml formaldehyde (37wt%) and the 6ml concentrated sulfuric acid are added in the 20ml ethanol together, the mol ratio of phenol monomer and aldehyde monomer is about 1: 4, stirring is dissolved it fully, with the above-mentioned solution 50ml autoclave of packing into, 120 ℃ of insulations 10 hours, synthetic reaction obtained porous polymer hydroquinones formaldehyde resin gel; The gained gel is smashed to pieces, 120 ℃ of temperature vacuumize 6 hours, vacuum degree is-0.1MPa, porous hydroquinones formaldehyde resin, the gained material is stand-by with the mortar grind into powder.
(2) configuration of the chloride solution of stanniferous
Configuration 10mL SnCl
2Solution, the concentration of tin is 3mol/L in the solution.
(3) preparation of stanniferous macromolecule resin
The porous polymer phenolic resins 6g that step (1) is made joins in the tin-salt solution of step (2), be that phenolic resins and pink salt mass ratio are 1: 1, soak after 3 hours, in solution, dropwise add the ammonia aqueous solution that 20mL concentration is 15wt%, vigorous stirring in the process that adds ammonia aqueous solution, obtain mixing suspension, the stannic hydroxide precipitation that generates enters in the hole of porous resin, mixing suspension is filtered, and wash with distilled water, 120 ℃ of vacuumize 6h, vacuum degree is-0.1MPa.
(4) preparation of tin carbon composite
With the dried mixture of step (3) under 5% hydrogen, 95% argon gas atmosphere protection; heat with 10 ℃/min heating rate; in 650 ℃ of following constant temperature calcinings 5 hours; make porous polymer phenolic resins carry out cracking and carburizing reagent, obtain the lithium ion battery tin carbon negative pole material that tin accounts for 39wt% at last.
The lithium ion battery tin carbon negative pole material of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF (Kynoar) respectively at 80: 10: 10, with NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry, evenly be coated on the Copper Foil, 80 ℃ of vacuumize 24 hours makes the Experimental cell pole piece.Be to electrode with the lithium sheet again, electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell, and under the condition of constant current 0.1C, carry out cycle performance and test, this material first discharge specific capacity is 520mAh/g, after 20 circulations, capacity is about 415mAh/g.
Embodiment three
(1) preparation of porous hydroquinones-catechol-benzaldehyde resin
With the 2.2g hydroquinones, 1.1g catechol, 6ml benzaldehyde, 5ml nitric acid adds in the 20ml deionized water together, the mol ratio of phenol monomer and aldehyde monomer is about 1: 2, stirs it is dissolved fully, with the above-mentioned solution reactor of packing into, 30 ℃ of insulations 30 days, the gained gel is smashed to pieces, 100 ℃ of vacuumize 12 hours, vacuum degree is-0.1MPa, get porous hydroquinones-catechol-benzaldehyde resin, the gained material is stand-by with the mortar grind into powder.
(2) configuration of the chloride solution of stanniferous
Configuration 30mL SnCl
45H
2O solution, the concentration of tin is 1mol/L in the solution.
(3) preparation of stanniferous macromolecule resin
The porous polymer phenolic resins 5g that step (1) is made joins in the tin-salt solution of step (2), be that phenolic resins and pink salt mass ratio are 1: 1.5, soak after 9 hours, in solution, dropwise add the ammonia aqueous solution that 10mL concentration is 30wt%, vigorous stirring in the process that adds ammonia aqueous solution, obtain mixing suspension, the stannic hydroxide precipitation that generates enters in the hole of porous resin, mixing suspension is filtered, and wash with distilled water, 100 ℃ of vacuumize 12h, vacuum degree is-0.1MPa.
(4) preparation of tin carbon composite
With the dried mixture of step (3) under nitrogen atmosphere protection; heat with 5 ℃/min heating rate; in 700 ℃ of following constant temperature calcinings 3 hours, make porous polymer phenolic resins carry out cracking and carburizing reagent, obtain the lithium ion battery tin carbon negative pole material that tin accounts for 51wt% at last.
The lithium ion battery tin carbon negative pole material of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF (Kynoar) respectively at 80: 10: 10, with NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry, evenly be coated on the Copper Foil, 80 ℃ of vacuumize 24 hours makes the Experimental cell pole piece.Be to electrode with the lithium sheet again, electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell, and under the condition of constant current 0.1C, carry out the cycle performance test, this material first discharge specific capacity is 548mAh/g.
Embodiment four
(1) preparation of porous hydroquinones acetaldehyde resin
With the 2.2g hydroquinones, 7ml acetaldehyde, 0.5g NaOH add in the 20ml deionized water together, and the mol ratio of phenol monomer and aldehyde monomer is about 1: 5, stirring is dissolved it fully, with the above-mentioned solution autoclave of packing into,, the gained gel is smashed to pieces 180 ℃ of insulations 0.5 hour, 100 ℃ of vacuumize 12 hours, vacuum degree is-0.1MPa, porous hydroquinones acetaldehyde resin, the gained material is stand-by with the mortar grind into powder.
(2) configuration of the chloride solution of stanniferous
Configuration 10mL SnCl
2Solution, the concentration of tin is 2mol/L in the solution.
(3) preparation of stanniferous macromolecule resin
The porous polymer phenolic resins 4g that step (1) is made joins in the tin-salt solution of step (2), be that phenolic resins and tin-salt solution mass ratio are 1: 2, soak after 6 hours, in solution, dropwise add the ammonia aqueous solution that 20mL concentration is 18wt%, vigorous stirring in the process that adds ammonia aqueous solution, obtain mixing suspension, the stannic hydroxide precipitation that generates enters in the hole of porous resin, mixing suspension is filtered, and wash with distilled water, 100 ℃ of vacuumize 10h, vacuum degree is-0.1MPa.
(4) preparation of tin carbon composite
With the dried mixture of step (3) under 95% nitrogen, 5% hydrogen atmosphere protection; heat with 10 ℃/min heating rate; in 750 ℃ of following constant temperature calcinings 1 hour; make porous polymer phenolic resins carry out cracking and carburizing reagent, obtain the lithium ion battery tin carbon negative pole material that tin accounts for 47wt% at last.
The lithium ion battery tin carbon negative pole material of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF (Kynoar) respectively at 80: 10: 10, with NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry, evenly be coated on the Copper Foil, 80 ℃ of vacuumize 24 hours makes the Experimental cell pole piece.Be to electrode with the lithium sheet again, electrolyte is EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution of 1mol/L LiPF6, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell, and under the condition of constant current 0.1C, carry out the cycle performance test, this material first discharge specific capacity is 485mAh/g.
Embodiment five
(1) preparation of expanded phenol-formaldehyde resin
With 0.94g phenol and 1.1g resorcinol, 2ml formaldehyde (37wt%), 2ml acetaldehyde, 2ml benzaldehyde, 1g sodium carbonate add in the 20ml deionized water together, and the mol ratio of phenol monomer and aldehyde monomer is about 1: 4, stirring is dissolved it fully, with the above-mentioned solution autoclave of packing into,, the gained gel is smashed to pieces 120 ℃ of insulations 6 hours, vacuumize is 10 hours under 100 ℃ of temperature, vacuum degree is-0.1MPa, expanded phenol-formaldehyde resin, the gained material is stand-by with the mortar grind into powder.
(2) configuration of the chloride solution of stanniferous
Configuration 10mL SnCl
2Solution, the concentration of tin is 4mol/L in the solution.
(3) preparation of stanniferous macromolecule resin
The porous polymer phenolic resins 2.7g that step (1) is made joins in the tin-salt solution of step (2), be that phenolic resins and pink salt mass ratio are 1: 3, soak after 4 hours, in solution, dropwise add the ammonia aqueous solution that 20mL concentration is 18wt%, vigorous stirring in the process that adds ammonia aqueous solution, obtain mixing suspension, the stannic hydroxide precipitation that generates enters in the hole of porous resin, mixing suspension is filtered, and wash with distilled water, 80 ℃ of vacuumize 16h, vacuum degree is-0.1MPa.
(4) preparation of tin carbon composite
With the dried mixture of step (3) under nitrogen atmosphere protection; heat with 3 ℃/min heating rate; in 750 ℃ of following constant temperature calcinings 3 hours, make porous polymer phenolic resins carry out cracking and carburizing reagent, obtain the lithium ion battery tin carbon negative pole material that tin accounts for 58wt% at last.
The lithium ion battery tin carbon negative pole material of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF (Kynoar) respectively at 80: 10: 10, with NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry, evenly be coated on the Copper Foil, 80 ℃ of vacuumize 24 hours makes the Experimental cell pole piece.Be to electrode with the lithium sheet again, electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell, and under the condition of constant current 0.1C, carry out the cycle performance test, this material first discharge specific capacity is 595mAh/g.
Embodiment six
(1) preparation of expanded phenol-formaldehyde resin
With 2.82g phenol, 3ml acetaldehyde, 3ml benzaldehyde, 0.5g potassium hydroxide adds in the 20ml deionized water together, the mol ratio of phenol monomer and aldehyde monomer is about 1: 3, stirs it is dissolved fully, with the above-mentioned solution autoclave of packing into, 150 ℃ of insulations 4 hours, the gained gel is smashed to pieces, and vacuumize is 10 hours under 100 ℃ of temperature, and vacuum degree is-0.1MPa, get expanded phenol-formaldehyde resin, the gained material is stand-by with the mortar grind into powder.
(2) configuration of the chloride solution of stanniferous
Configuration 10mL SnCl
4And SnCl
2Mixture solution, the concentration of tin is 3mol/L in the solution.
(3) preparation of stanniferous macromolecule resin
The porous polymer phenolic resins 4g that step (1) is made joins in the tin-salt solution of step (2), be that phenolic resins and pink salt mass ratio are about 1: 2, soak after 6 hours, in solution, dropwise add the ammonia aqueous solution that 20mL concentration is 18wt%, vigorous stirring in the process that adds ammonia aqueous solution, obtain mixing suspension, the stannic hydroxide precipitation that generates enters in the hole of porous resin, mixing suspension is filtered, and wash with distilled water, 120 ℃ of vacuumize 10h, vacuum degree is-0.1MPa.
(4) preparation of tin carbon composite
With the dried mixture of step (3) under argon gas atmosphere protection; heat with 6 ℃/min heating rate; in 700 ℃ of following constant temperature calcinings 4 hours, make porous polymer phenolic resins carry out cracking and carburizing reagent, obtain the lithium ion battery tin carbon negative pole material that tin accounts for 64wt% at last.
The lithium ion battery tin carbon negative pole material of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF (Kynoar) respectively at 80: 10: 10, with NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry, evenly be coated on the Copper Foil, 80 ℃ of vacuumize 24 hours makes the Experimental cell pole piece.Be to electrode with the lithium sheet again, electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell, and under the condition of constant current 0.1C, carry out the cycle performance test, this material first discharge specific capacity is 538mAh/g.
By above detailed description to the embodiment of the invention, can understand the low difficult situation of lithium ion battery negative material lithium storage content that the invention solves, simultaneously tinbase composite material cycle performance is improved, can effectively avoid the powder of detached of material in the charge and discharge process that bulk effect causes.And solved the problem of tinbase Composite Preparation difficulty in the past.
Be understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (10)
1. used as negative electrode of Li-ion battery tin carbon composite is characterized in that:
Adopt the carbon matrix raw material source of porous polymer phenolic resins as composite cathode material of lithium ion battery, adopt the tin matter raw material source of stanniferous chloride aqueous solution as composite cathode material of lithium ion battery, utilize the pore space structure of porous polymer phenolic resins, this porous polymer phenolic resins is placed the stanniferous chloride aqueous solution, forming the stannic hydroxide precipitation by the adding ammonia aqueous solution in the stanniferous chloride aqueous solution is filled in the hole, make it that the cracking and the carburizing reagent of porous polymer phenolic resins take place through high-temperature roasting, obtain the tin carbon composite, wherein tin content is 35-70wt%.
2. used as negative electrode of Li-ion battery tin carbon composite according to claim 1 is characterized in that: described porous polymer phenolic resins contains the mesoporous of the micropore of 0.4-1nm and 2-50nm, pore volume 0.4-2.4cm
3g
-1, specific surface 450-1000m
2g
-1
3. used as negative electrode of Li-ion battery tin carbon composite according to claim 1, it is characterized in that described porous polymer phenolic resins is is 1 with phenol monomer and aldehyde monomer in molar ratio: 1-1: 5 are dissolved in the solvent, wherein the concentration of phenol monomer is 0.5-1.5mol/L, the aldehyde monomer is 0.5-2.5mol/L, add acid or alkali and make catalyst, through reacting synthetic porous polymer.
4. used as negative electrode of Li-ion battery tin carbon composite according to claim 3 is characterized in that: described phenol monomer is one or more in phenol, hydroquinones, catechol, the resorcinol; Described aldehyde monomer is one or more in acetaldehyde, formaldehyde and the benzaldehyde; Described solvent is water or ethanol; Described acid is a kind of in hydrochloric acid, sulfuric acid, the nitric acid; Described alkali is a kind of in NaOH, potassium hydroxide, the sodium carbonate.
5. according to the arbitrary described used as negative electrode of Li-ion battery tin carbon composite of claim 1-4, it is characterized in that: described stanniferous villaumite is at least a in stannous chloride, butter of tin, the stannic chloride pentahydrate, and the concentration of tin is 1-4mol/L in the stanniferous chloride aqueous solution.
6. used as negative electrode of Li-ion battery tin carbon composite according to claim 1 is characterized in that: described high-temperature roasting is 600-750 ℃ of following constant temperature calcining 1-10 hour.
7. the preparation method of a used as negative electrode of Li-ion battery tin carbon composite is characterized in that, may further comprise the steps:
(1) preparation porous polymer phenolic resins
The raw material of preparation porous polymer resin is phenol monomer and aldehyde monomer, with phenol monomer and aldehyde monomer is 1 in molar ratio: 1-1: 5 are dissolved in the solvent, wherein the concentration of phenol monomer is 0.5-1.5mol/L, the aldehyde monomer is 0.5-2.5mol/L, add acid or alkali and make catalyst, when making catalyst with acid, the concentration of acid is at 0.1-5mol/L; When making catalyst with alkali, the concentration of alkali is at 0.1-2mol/L, and synthetic reaction obtains porous polymer phenolic resins.
Smash to pieces behind the product natural cooling, 80-120 ℃ vacuumize 6-18 hour, vacuum degree is-0.1MPa, it is stand-by to clay into power in the mortar, synthetic porous polymer contains the mesoporous of the micropore of 0.4-1nm and 2-50nm, pore volume is 0.4-2.4cm
3g
-1, specific surface is up to 450-1000m
2g
-1
(2) chloride solution of configuration stanniferous
Accurately a certain amount of stanniferous villaumite of weighing is dissolved in the deionized water, and the concentration of tin is 1-4mol/L in the solution;
(3) preparation stanniferous macromolecule phenolic resins
The porous polymer phenolic resins that step (1) is made joins in the tin-salt solution of step (2), the mass ratio of porous polymer phenolic resins and pink salt is 1: 1-1: 3, after soaking 3-9 hour, the ammonia aqueous solution that in solution, dropwise adds 15-30wt%, vigorous stirring in the process that adds ammonia aqueous solution, add ammonia aqueous solution amount calculate by the pink salt in whole precipitation solutions and excessive a little, get mixing suspension, again after filtration, and wash with distilled water, 80-120 ℃ vacuumize 6-18 hour, vacuum degree is-0.1MPa, obtains the stanniferous macromolecule phenolic resins in the hole that stannic hydroxide is deposited in porous polymer phenolic resins;
(4) preparation tin carbon composite
With the dried mixture of step (3) under protective atmosphere; heat with 1-10 ℃/min heating rate; in 600-750 ℃ of following constant temperature calcining 1-10 hour, carry out the cracking and the carburizing reagent of porous polymer phenolic resins, obtain the used as negative electrode of Li-ion battery tin carbon composite that tin accounts for 35-70%.
8. the preparation method of used as negative electrode of Li-ion battery tin carbon composite according to claim 7, it is characterized in that in the step (1) that synthetic reaction is with the reactant sealing insulation in the reactor of packing into, temperature is in 30-180 ℃ of scope in the reactor, temperature retention time is 0.5 hour to 30 days, when temperature surpasses solvent boiling point, feed with autoclave.
9. the preparation method of used as negative electrode of Li-ion battery tin carbon composite according to claim 7, it is characterized in that protective atmosphere is the mist of inert gas or reducing gas and inert gas described in the step (4), described inert gas is a kind of in argon gas or the nitrogen; Reducing gas is a hydrogen.
10. a lithium ion battery is characterized in that: press the resulting tin carbon composite of the arbitrary described preparation method of claim 7-9 as lithium ion battery negative material.
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