CN102231439B - Sulfur-carbon composite material for cathode of lithium ion battery, preparation method and lithium ion battery - Google Patents
Sulfur-carbon composite material for cathode of lithium ion battery, preparation method and lithium ion battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000011593 sulfur Substances 0.000 claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 229920001568 phenolic resin Polymers 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000005011 phenolic resin Substances 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 150000001299 aldehydes Chemical class 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 claims description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 230000001681 protective effect Effects 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
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- 239000000376 reactant Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000004567 concrete Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 27
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 14
- 239000006260 foam Substances 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002898 organic sulfur compounds Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- -1 sodium metals Chemical class 0.000 description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 3
- VZQBDGHUOBRFAA-UHFFFAOYSA-N 2-(2,6-dihydroxyphenyl)benzaldehyde Chemical compound C1(O)=C(C(O)=CC=C1)C1=CC=CC=C1C=O VZQBDGHUOBRFAA-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 description 1
- 241001466460 Alveolata Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241001529297 Coregonus peled Species 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 150000001721 carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage 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 sulfur-carbon composite material for the cathode of a lithium ion battery, a preparation method, and the lithium ion battery assembled by taking the sulfur-carbon composite material produced by the method as an electrode. The sulfur-carbon composite material consists of two parts which are a porous sulfur-containing macromolecular polymer and elementary sulfur respectively, wherein the porous sulfur-containing macromolecular polymer has high electric conductivity, and is used for holding sulfur and small molecular sulfides generated in an electrolysis process; and the elementary sulfur has electrochemical activity. The sulfur-carbon composite material can serve as the cathode material of the lithium ion battery, and has the sulfur content of 30 to 60 weight percent.
Description
Technical field
The present invention relates to battery manufacture technical field, be specifically related to a kind of sulfur-carbon composite material for cathode of lithium ion battery and preparation method thereof and lithium ion battery.
Background technology
At present, Environment and energy problem causes people's concern day by day, and the energy of environment-friendly high-efficiency is more and more in good graces.Electric energy can be described as the of paramount importance energy in the world today, and battery also receives vast scientific research person's concern and caused " the battery revolution " of one another as the important composition of electric energy and file layout because be.The performance advantages such as energy density is high, have extended cycle life make lithium ion battery become the most rising storage battery system, as a kind of high performance secondary green battery, in various portable type electronic products and communication tool, are widely used.The specific capacity of lithium metal can reach 3861mAh/g, is the highest in existing negative material.And that the bottleneck that restriction lithium battery specific capacity improves is the specific capacity of positive electrode is lower.Therefore, particularly the research of positive electrode is most crucial for novel battery material.
Elemental sulfur has height ratio capacity as anode material of lithium battery, hypotoxicity, the advantage such as cheap.Specific capacity can be up to 1675mAh/g, theoretical voltage 2.287v, and theoretical energy density reaches 3824Wh/kg, can be described as extrahigh energy material, is that in current the understood positive electrode of people, specific capacity is the highest, in addition, also has advantages of cheapness, low toxicity.Thereby lithium-sulfur cell system was just subject to the people's attention as far back as last century 70, the eighties, at present due to global energy problem, so high specific energy is very attractive, based on advantages such as low equivalent ratio, low price, environmental protection, elemental sulfur and sulfur compound have been subject to extensive concern in the research field of energy storage material.
Since long period, people have carried out a lot of research to elemental sulfur and sulfur compound as the positive electrode of high power capacity, but these materials still exist a lot of problems.First, the conductivity of elemental sulfur itself is very poor, must add a large amount of conductive agents to increase its conductivity, and the energy density of electrode is just greatly reduced; Secondly, concerning elemental sulfur as the positive pole of active material, although the Li of the elementary sulfur existing on positive pole while charging completely and existence while discharging completely
2s is insoluble in polarity organic electrolyte, but many lithium sulfides that during part charging and discharging state, positive pole contains are soluble in polarity electrolyte, same, the little molecular sulfur compound producing during polymeric organosulfides electric discharge is also soluble in organic electrolyte, and in negative pole deposition, affect the cycle performance of battery.R.D.Rauh etc. think and dissolve in the stability that many lithium sulfides in electrolyte do not affect lithium metal to possess possibility (J.Electrochem.Soc.1979,126 (4): 523-527) of making secondary cell.Yamin and Peled etc. have studied the electrochemical reaction mechanism of many lithium sulfides, think that its process that is reduced to rudimentary sulfide is very complicated, have both comprised the electrochemical process of multistep electron exchange, also have the chemical conversion between sulfide.Therefore, how improving the conductivity of material, and solve the dissolution problems that discharges and recharges intermediate product, improve cycle performance of battery, is the research emphasis of sulfenyl positive electrode.
Carbon sulphur polymer can obtain higher specific capacity.The CS such as Skotheim
2(USP 5601947 in solvent, with sodium metal reduction, to generate poly-nitric sulfid (Polycarbon Sulfide), 1997), again acetylene and elemental sulfur are reacted in Sodamide liquid ammonia solution and generate polyacetylene copolymerization sulphur (Polyacetylene-co-Polysulfur) (USP 6117590,2000), put first specific capacity and can reach 800-1000mAh/g.This two classes electrode material is all still mixture not bery clearly of structure, in synthetic, use a large amount of sodium metals, reaction condition requires harsh, process is more numerous and diverse, what have comprises a large amount of little molecules, in some main chains, containing the structure of S-S, the easily molten mistake of depolymerization when electric discharge, causes anodal disintegration, cycle performance to decline.
People's (United States Patent (USP)s 4833048 and 4917974 such as D Jonghe; J.Eletrochem.Soc., 1991,138 (7): 189-1895) put forward a series of organic sulfur compounds with a plurality of sulfenyls, but many organic sulfur compounds can only carry out reversible discharging and recharging at 90 ℃.Reason is that at room temperature electron transfer rate is very slow for the disulfide only consisting of aliphat.In these organic sulfur compounds, better performances be DMcT (2,5-disulfide group, 1,3,4-thiadiazoles).But this material require at high temperature reacts and poorly conductive, limited the application of these organic sulfur compounds.
Current Research Thinking is the composite material that preparation is comprised of sulfenyl material and the material that possesses adsorptivity and conductivity, take conducting polymer or conductive structure as main chain, to improve conductivity and the structural stability of positive electrode, and occur on redox sulfur-containing group is connected to main chain carbon atom in the mode of side chain or composite material is made in sulfur compound and conducting polymer blend, during electric discharge, skeleton is not degraded, thereby guarantee that anodal external form is stablized and most of sulphur is trapped in positive polar region, cyclicity will strengthen to some extent.Chinese patent CN1214074C, CN1242505C reported elemental sulfur and the organic polymer compound elemental sulfur/conducting polymer composite material that is prepared at high temperature, and organic polymer used is that polypropylene, polypropylene are fine, any one in polystyrene, polyethylene glycol oxide or polyvinyl alcohol.With this composite material in lithium battery for the second time specific discharge capacity can reach 800mAh/g, through 50 times circulation after, more than specific capacity remains on 600mAh/g.But the raw polymer of mentioning in above-mentioned patent is more expensive, be difficult to embody lithium-sulfur cell advantage with low cost, too high for industrial production cost, and along with the increase of cycle-index, cyclical stability is not fine.
In a word in existing cell positive material manufacture method, all more or less exist complex process, cost high, be difficult to the shortcomings such as large-scale production.Therefore the sulfur-bearing positive electrode that, develop that a kind of technique is simple, cost is low, is easy to industrialization is one of lithium sulfur battery anode material field difficult problem that will solve.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provide that a kind of raw material is cheap and easy to get, specific capacity is high, good cycling stability for the sulphur carbon composite of lithium ion cell positive and preparation method and the lithium ion battery of this composite material.The sulphur carbon composite function admirable obtaining, synthesis technique is simple simultaneously, and cost is low, is easy to industrialization.
Chinese Patent Application No.: 200910174696.9 have introduced a kind of Hydrophilous porous phenolic resin, its structure includes the mesoporous of the micropore of 0.4-1nm and 2-50nm, this Hydrophilous porous phenolic resin adsorbance is large, is mainly used in precious metal smelting and reclaims field selective absorption precious metal ion.The present invention makes sulfur-carbon composite material for cathode of lithium ion battery by this Hydrophilous porous phenolic resin for field of batteries.
Therefore; the technical scheme that solution the technology of the present invention problem adopts is that this sulfur-carbon composite material for cathode of lithium ion battery be take organic polymer as matrix; described sulphur carbon composite is organic polymer and the compounded organic sulfur carbide of elemental sulfur roasting under protective atmosphere; sulfur content is 30-60wt%, and organic polymer used is porous polymer phenolic resins.Be that the present invention adopts a kind of porous polymer phenolic resins as the carbonaceous raw material source of sulphur carbon composite; this macromolecule phenolic resins contains hydroxyl and has special loose structure; this macromolecule phenolic resins is mixed by certain mass ratio with sulphur powder, then high-temperature roasting under protective atmosphere.In the process of processing in high-temperature roasting, sub-fraction sulphur enters on the product strand after phenolic resin carbonized and generates sulfur-containing polymer; Most of sulphur fusing has entered in the special hole of this material, obtained the sulphur carbon composite of function admirable, and sulphur is uniformly dispersed in porous sulphur carbon composite.This sulphur carbon composite can be used as the positive electrode of lithium ion battery.
Further preferably, in described sulphur carbon composite, sulfur content is 40-50wt%.
Further preferably, the micropore that described macromolecule phenolic resins contains 0.4-1nm and 2-50nm's is mesoporous, pore volume 0.4-2.4cm
3g
-1, specific surface 450-1000m
2g
-1.
The preparation method of sulfur-carbon composite material for cathode of lithium ion battery of the present invention, first prepares porous polymer phenolic resins, more compound under high-temperature roasting with sulphur powder, prepares sulfur-bearing carbon composite anode material.Specifically comprise the following steps:
(1) prepare porous polymer phenolic resins
The raw material of preparing porous polymer resin is phenol monomer and aldehyde monomer, by phenol monomer and aldehyde monomer, be 1 in molar ratio: 1-1: 5 are dissolved in solvent, wherein the concentration of phenol monomer is 0.5-1.5mol/L, aldehyde monomer is 0.5-2.5mol/L, add acid or alkali to make catalyst, while making catalyst with acid, the concentration of acid is at 0.1-5mol/L; While making catalyst with alkali, the concentration of alkali is at 0.1-2mol/L, and synthetic reaction obtains porous polymer phenolic resins, and its hole comprises that the micropore of 0.4-1nm and 2-50nm's is mesoporous.
Further preferably described phenol monomer is one or more in phenol, hydroquinones, catechol, resorcinol.Described aldehyde monomer is one or more in acetaldehyde, formaldehyde and benzaldehyde.Described solvent is water or ethanol.
Preferably, pack reactant in reactor sealing thermal insulation, in reactor, temperature is within the scope of 30-180 ℃, and temperature retention time is 0.5 hour to 30 days, when temperature surpasses solvent boiling point, with autoclave, feeds.
After product is naturally cooling, smash to pieces, 80-120 ℃ of vacuumize 6-18 hour, vacuum degree-0.1MPa, stand-by with mortar grind into powder.The micropore that synthetic porous polymer contains 0.4-1nm and 2-50nm's is mesoporous, pore volume 0.4-2.4cm
3g
-1, specific surface is 450-1000m
2g
-1.
(2) prepare sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained and sulphur powder in mass ratio 1: 1-1: 3 evenly mix; under protective atmosphere; with 1-10 ℃/min heating rate, heat; constant temperature calcining 1-6 hour at 250-400 ℃; at this temperature; overwhelming majority phenolic resin carbonized; elemental sulfur fusing enters after carbonization in carbon back hole; separately having a small amount of sulphur to react with expanded phenol-formaldehyde resin enters in product strand; form carbon sulfur bond; obtain the sulphur carbon composite of the elemental sulfur/sulfur-containing polymer of function admirable, and sulphur is uniformly dispersed in porous sulphur carbon composite.
Preferably, described protective atmosphere can be the mist of inert gas or reducing gas and inert gas, and described inert gas is a kind of in argon gas or nitrogen; Reducing gas is hydrogen.
The invention has the beneficial effects as follows:
(1) product particle is tiny and be evenly distributed.Due to the special nano-pore structure of synthetic porous polymer phenolic resins, compound with sulphur after, the structure of material is not have vicissitudinously substantially, a part of sulphur is evenly distributed in hole.
(2) chemical property of product is good.After tested the synthetic elemental sulfur/sulfur-containing polymer composite material of the present invention first discharge capacity reached 670mAh/g, after 80 discharge cycles, capacity still remains on 450mAh/g left and right.
(3) simple, the processing ease of preparation technology, cost of material is low, equipment investment is less.
Accompanying drawing explanation
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;
The prepared material of Fig. 2 embodiment mono-is made into the cycle performance figure under constant current 50mA/g after button cell.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment mono-
(1) preparation of porous catechol formaldehyde resin
2.20g catechol, 2m1 formaldehyde are added in 10ml ethanol together with 5ml concentrated hydrochloric acid, stirring is dissolved it completely, pack above-mentioned solution into 50ml autoclave, 100 ℃ of insulations 5 hours, synthetic reaction obtained porous polymer catechol formaldehyde resin gel; Gained gel is smashed to pieces, 80 ℃ of temperature vacuumize 12 hours, and vacuum degree-0.1MPa, resulting materials is stand-by with mortar grind into powder.
The phenolic resins stereoscan photograph of gained is as shown in Fig. 1 a, b, can find out that sample is alveolate texture, the small and dense collection of hole, some independently circular cavities are distributing can see sample in low multiple picture in, and can find out its inner surface smoother, the micropore that synthetic expanded phenol-formaldehyde resin polymer contains 0.4-1nm and 2-50nm's is mesoporous, pore volume 2.4cm
3g
-1, specific surface 1000m
2g
-1.
(2) preparation of sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained evenly mixes by quality with sulphur powder at 1: 1; under argon shield, with the heating of 5 ℃/min heating rate, at 350 ℃, constant temperature calcining is 2 hours; obtain elemental sulfur/sulfur-containing polymer composite material, its sulfur content is 42.55wt%.
The positive electrode of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PTFE respectively at 70: 20: 10, add alcohol solvent, grind evenly, become paste, then roll on nickel foam collector (nickel foam substrate is first weighed), put at 80 ℃ of vacuum drying chambers and toast 12h, vacuum degree-0.1MPa, makes positive plate.Negative pole adopts metal lithium sheet, and barrier film is selected PE micro-pore septum, and electrolyte is 1.5mol/LLiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is 2: 1).In being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell.And to carry out cycle performance test under the condition of electric current 50mA/g, this material first discharge specific capacity is 670mAh/g, after 80 circulations, capacity is about 452mAh/g, as shown in Figure 2.
Embodiment bis-
(1) preparation of porous hydroquinones formaldehyde resin
3.30g hydroquinones, 12ml formaldehyde are added in 20ml ethanol together with 6ml concentrated hydrochloric acid, stirring is dissolved it completely, pack above-mentioned solution into 50ml autoclave, 120 ℃ of insulations 10 hours, gained gel is smashed to pieces to 100 ℃ of temperature vacuumize 12 hours, vacuum degree-0.1MPa, obtain porous hydroquinones formaldehyde resin, resulting materials is stand-by with mortar grind into powder.
(2) preparation of sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained evenly mixes in mass ratio with sulphur powder at 1: 2; under argon shield, with the heating of 5 ℃/min heating rate, at 300 ℃, constant temperature calcining is 2 hours; obtain elemental sulfur/sulfur-containing polymer composite material, its sulfur content is 47.08wt%.
The positive electrode of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PTFE respectively at 70: 20: 10, add alcohol solvent, grind evenly, become paste, then roll on nickel foam collector (nickel foam substrate is first weighed), put at 80 ℃ of vacuum drying chambers and toast 12h, make positive plate.Negative pole adopts metal lithium sheet, and barrier film is selected PE micro-pore septum, and electrolyte is 1.5mol/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is 2: 1).In being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell.And to carry out cycle performance test under the condition of electric current 50mA/g, this material first discharge specific capacity is 692mAh/g.
Embodiment tri-
(1) preparation of porous phenol-formaldehyde resin
2.82g phenol 6ml formaldehyde is added in 20ml deionized water together with 0.5g NaOH, stirring is dissolved it completely, pack above-mentioned solution into 50ml autoclave, 150 ℃ of insulations 5 hours, gained gel is smashed to pieces to 120 ℃ of temperature vacuumize 6 hours, vacuum degree-0.1MPa, obtain porous phenol-formaldehyde resin, resulting materials is stand-by with mortar grind into powder.
(2) preparation of sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained evenly mixes in mass ratio with sulphur powder at 1: 3; under the gaseous mixture protection of 95% argon gas 5% hydrogen; with 5 ℃/min heating rate, heat; at 400 ℃, constant temperature calcining is 1 hour; obtain elemental sulfur/sulfur-containing polymer composite material, its sulfur content is 41wt%.
The positive electrode of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PTFE respectively at 70: 20: 10, add alcohol solvent, grind evenly, become paste, then roll on nickel foam collector (nickel foam substrate is first weighed), put at 80 ℃ of vacuum drying chambers and toast 12h, make positive plate.Negative pole adopts metal lithium sheet, and barrier film is selected PE micro-pore septum, and electrolyte is 1.5mol/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is 2: 1).In being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell.And to carry out cycle performance test under the condition of electric current 50mA/g, this material first discharge specific capacity is 585mAh/g.
Embodiment tetra-
(1) preparation of porous phenol-catechol-formaldehyde resin
By 1.88g phenol, 1.1g catechol, 4ml formaldehyde, 0.5g potassium hydroxide adds in 20 deionized waters together, stirs it is dissolved completely, pack above-mentioned solution into autoclave, 100 degree insulation 10 hours, gained gel is smashed to pieces to 100 ℃ of temperature vacuumize 12 hours, obtain porous phenol-catechol-formaldehyde resin, resulting materials is stand-by with mortar grind into powder.
(2) preparation of carbon/sulphur composite material
The macromolecule phenolic resins that step (1) is obtained evenly mixes in mass ratio with sulphur powder at 1: 2; under argon shield, with the heating of 5 ℃/min heating rate, at 350 ℃, constant temperature calcining is 2 hours; obtain elemental sulfur/sulfur-containing polymer composite material, its sulfur content is 45.20wt%.
The positive electrode of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PTFE respectively at 70: 20: 10, add alcohol solvent, grind evenly, become paste, then roll on nickel foam collector (nickel foam substrate is first weighed), put at 80 ℃ of vacuum drying chambers and toast 12h, make positive plate.Negative pole adopts metal lithium sheet, and barrier film is selected PE micro-pore septum, and electrolyte is 1.5mol/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is 2: 1).In being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell.And to carry out cycle performance test under the condition of electric current 50mA/g, this material first discharge specific capacity is 653mAh/g.
Embodiment five
(1) preparation of porous resorcinol benzaldehyde resin
By 2g resorcinol, 4ml benzaldehyde, 5ml hydrochloric acid adds in 20ml deionized water together, stirring was dissolved it completely, packs above-mentioned solution into autoclave, 120 degree insulation 10 hours, gained gel is smashed to pieces, 100 ℃ of temperature vacuumize 12 hours, obtains porous resorcinol benzaldehyde resin, and resulting materials is stand-by with mortar grind into powder.
(2) preparation of sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained evenly mixes in mass ratio with sulphur powder at 1: 1; under argon shield, with the heating of 5 ℃/min heating rate, at 300 ℃, constant temperature calcining is 4 hours; obtain elemental sulfur/sulfur-containing polymer composite material, its sulfur content is 40.40wt%.
The positive electrode of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PTFE respectively at 70: 20: 10, add alcohol solvent, grind evenly, become paste, then roll on nickel foam collector (nickel foam substrate is first weighed), put at 80 ℃ of vacuum drying chambers and toast 12h, make positive plate.Negative pole adopts metal lithium sheet, and barrier film is selected PE micro-pore septum, and electrolyte is 1.5mol/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is 2: 1).In being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell.And to carry out cycle performance test under the condition of electric current 50mA/g, this material first discharge specific capacity is 612mAh/g.
Embodiment six
(1) preparation of expanded phenol-formaldehyde resin
3.30g hydroquinones, 4ml formaldehyde, 4ml acetaldehyde, 4ml benzaldehyde are added in 20ml deionized water together with 6ml red fuming nitric acid (RFNA), stirring is dissolved it completely, pack above-mentioned solution into 50ml reactor, 30 ℃ of insulations 30 days, gained gel is smashed to pieces to 120 ℃ of temperature vacuumize 18 hours, vacuum degree-0.1MPa, obtain expanded phenol-formaldehyde resin, resulting materials grind into powder is stand-by.
(2) preparation of sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained evenly mixes in mass ratio with sulphur powder at 1: 3; under nitrogen protection, with the heating of 1 ℃/min heating rate, at 250 ℃, constant temperature calcining is 6 hours; obtain elemental sulfur/sulfur-containing polymer composite material, its sulfur content is 58.7wt%.
The positive electrode of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PTFE respectively at 70: 20: 10, add alcohol solvent, grind evenly, become paste, then roll on nickel foam collector (nickel foam substrate is first weighed), put at 120 ℃ of vacuum drying chambers and toast 18h, make positive plate.Negative pole adopts metal lithium sheet, and barrier film is selected PE micro-pore septum, and electrolyte is 1.5mol/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is 2: 1).In being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell.And to carry out cycle performance test under the condition of electric current 50mA/g, this material first discharge specific capacity is 918mAh/g.
Embodiment seven
(1) preparation of expanded phenol-formaldehyde resin
3.30g hydroquinones, 5ml formaldehyde, 5ml acetaldehyde are added in 20ml ethanol together with 0.8g sodium carbonate, stirring is dissolved it completely, pack above-mentioned solution into 50ml autoclave, at 180 ℃ of insulation 0.5h, gained gel is smashed to pieces to 120 ℃ of temperature vacuumize 6 hours, vacuum degree-0.1MPa, obtain expanded phenol-formaldehyde resin, resulting materials is stand-by with mortar grind into powder.
(2) preparation of sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained evenly mixes in mass ratio with sulphur powder at 1: 3; under 95% nitrogen 5% hydrogen atmosphere protection; with 10 ℃/min heating rate, heat; at 250 ℃, constant temperature calcining is 6 hours; obtain elemental sulfur/sulfur-containing polymer composite material, its sulfur content is 55.3wt%.
The positive electrode of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PTFE respectively at 70: 20: 10, add alcohol solvent, grind evenly, become paste, then roll on nickel foam collector (nickel foam substrate is first weighed), put at 120 ℃ of vacuum drying chambers and toast 18h, make positive plate.Negative pole adopts metal lithium sheet, and barrier film is selected PE micro-pore septum, and electrolyte is 1.5mol/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is 2: 1).In being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell.And to carry out cycle performance test under the condition of electric current 50mA/g, this material first discharge specific capacity is 892mAh/g.
By the above detailed description to the embodiment of the present invention, can understand the poor difficult situation of lithium-sulfur cell cycle performance that the invention solves, product chemical property is good simultaneously, has solved the problem of lithium-sulfur cell negative pole deposition in the past.
Be understandable that, above execution mode is only used to principle of the present invention is described and the illustrative embodiments that adopts, 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 are also considered as protection scope of the present invention.
Claims (9)
1. a preparation method for sulfur-carbon composite material for cathode of lithium ion battery, is characterized in that, comprises following concrete steps:
(1) prepare porous polymer phenolic resins
The raw material of preparing porous polymer phenolic resins is phenol monomer and aldehyde monomer, by phenol monomer and aldehyde monomer in molar ratio for 1:1-1:5 is dissolved in solvent, wherein the concentration of phenol monomer is 0.5-1.5mol/L, aldehyde monomer is 0.5-2.5mol/L, add acid or alkali to make catalyst, while making catalyst with acid, the concentration of acid is at 0.1-5mol/L; While making catalyst with alkali, the concentration of alkali is at 0.1-2mol/L, and synthetic reaction obtains porous polymer phenolic resins;
After product is cooling, smash to pieces, 80-120 ℃ of vacuumize 6-18 hour, vacuum degree is-0.1MPa, and stand-by with mortar grind into powder, the micropore that synthetic porous polymer resin contains 0.4-1nm and 2-50nm's is mesoporous, and pore volume is 0.4-2.4cm
3g
-1, specific surface 450-1000m
2g
-1;
(2) prepare sulphur carbon composite
The macromolecule phenolic resins that step (1) is obtained and sulphur powder in mass ratio 1:1-1:3 evenly mix, and under protective atmosphere, with the heating of 1-10 ℃/min heating rate, constant temperature calcining 1-6 hour at 250-400 ℃, obtains sulphur carbon composite.
2. the preparation method of sulphur carbon composite according to claim 1, is characterized in that, the sulfur content of described sulphur carbon composite is 30-60wt%.
3. the preparation method of sulphur carbon composite according to claim 1, is characterized in that, the sulfur content of described sulphur carbon composite is 40-50wt%.
4. the preparation method of sulphur carbon composite according to claim 1, is characterized in that described in step (1), phenol monomer is: in phenol, hydroquinones, catechol, resorcinol at least one.
5. the preparation method of sulphur carbon composite according to claim 1, is characterized in that described in step (1), aldehyde monomer is: in acetaldehyde, formaldehyde and benzaldehyde at least one; Described solvent is: a kind of in water or ethanol;
6. the preparation method of sulphur carbon composite according to claim 1, is characterized in that described in step (1), acid is: a kind of in hydrochloric acid, sulfuric acid, nitric acid; Described alkali is: a kind of in NaOH, potassium hydroxide, sodium carbonate.
7. according to the preparation method of the arbitrary described sulphur carbon composite of claim 1-6, it is characterized in that described in step (2), protective atmosphere is the mist of inert gas or reducing gas and inert gas, described inert gas is a kind of in argon gas or nitrogen; Reducing gas is hydrogen.
8. the preparation method of sulphur carbon composite according to claim 7, it is characterized in that in step (1), synthetic reaction is to pack reactant in reactor sealing thermal insulation, in reactor, temperature is within the scope of 30-180 ℃, temperature retention time is 0.5 hour to 30 days, when temperature surpasses solvent boiling point, with autoclave, feed.
9. a lithium ion battery, is characterized in that: the resulting sulphur carbon composite of preparation method described in arbitrary by claim 1-8 is as anode material for lithium-ion batteries.
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| CN104630575B (en) * | 2015-02-02 | 2017-03-15 | 中国科学院化学研究所 | A kind of preparation of lithium metal secondary battery alloy electrode material and application |
| CN104821394B (en) * | 2015-04-03 | 2017-10-27 | 奇瑞汽车股份有限公司 | A kind of preparation method and applications of height ratio capacity sulfur-bearing positive electrode |
| CN106159264A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of preparation method of nitrogenous many nitric sulfids positive electrode |
| CN104835966B (en) * | 2015-04-30 | 2018-08-14 | 奇瑞汽车股份有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN107834043B (en) * | 2017-10-31 | 2020-05-08 | 奇瑞汽车股份有限公司 | Lithium-sulfur battery positive electrode material, preparation method and lithium-sulfur battery |
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| CN101850959A (en) * | 2010-05-31 | 2010-10-06 | 奇瑞汽车股份有限公司 | Method for preparing silicon-carbon cathode material of lithium ion battery |
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| US5690702A (en) * | 1995-06-07 | 1997-11-25 | Moltech Corporation | Method of making electroactive high storage capacity polycarbon-sulfide materials and electrolytic cells containing same |
| CN1396202A (en) * | 2002-04-17 | 2003-02-12 | 中国科学院上海微系统与信息技术研究所 | Sulfur/electric conducting polymer composition used as positive electrode of electrochemical power supply and its method |
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