CN1691381A - Preparation of lithium battery anode material carbon polysulfide alkyne - Google Patents
Preparation of lithium battery anode material carbon polysulfide alkyne Download PDFInfo
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- CN1691381A CN1691381A CNA2004100376976A CN200410037697A CN1691381A CN 1691381 A CN1691381 A CN 1691381A CN A2004100376976 A CNA2004100376976 A CN A2004100376976A CN 200410037697 A CN200410037697 A CN 200410037697A CN 1691381 A CN1691381 A CN 1691381A
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- Prior art keywords
- carbyne
- polysulfide
- preparation
- lithium
- lithium battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 29
- 239000005077 polysulfide Substances 0.000 title claims abstract description 29
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010405 anode material Substances 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 5
- 229910052799 carbon Inorganic materials 0.000 title description 5
- 150000001345 alkine derivatives Chemical class 0.000 title 1
- VRLIPUYDFBXWCH-UHFFFAOYSA-N hydridocarbon(.) Chemical compound [CH] VRLIPUYDFBXWCH-UHFFFAOYSA-N 0.000 claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- -1 hydrogen halides Chemical class 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 230000004087 circulation Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract 1
- 239000012433 hydrogen halide Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012047 saturated solution Substances 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
- 239000007787 solid Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a process for the preparation of a carbyne polysulfide. Removing hydrogen halide in molecules by using hydrogen-containing polyhalogenated olefin under the action of alkali to prepare carbyne, and heating and reacting the obtained carbyne with elemental sulfur under the protection of inert gas to prepare the carbyne polysulfide. The present invention provides primary and secondary lithium batteries using carbyne polysulfide as the positive electrode material, which have very high specific energy.
Description
Affiliated technical field
The present invention relates to the preparation of carbyne polysulfide and make the lithium battery of positive electrode with it.
Background technology
The height ratio capacity positive electrode is the key technology that improves the lithium battery performance, and the organic material of sulfur-bearing-sulfide linkage is an important kind wherein, and it carries out exoergic and energy storage by the fracture and the bonding of sulphur-sulfide linkage.It is RSSR (M.Liu et al.Electrode kinetics of organodisulfide cathodes forstorage batteries that people such as De Jonghe have successively reported expression formula, J.Electrochem.Soc.137 (3), 750 1990) and [R (S)
y]
n(L.C.De Jongheet al, Metal-Sulfur type cell having improved positive electrode, US Patent 4,833,0481989) organosulfur compound positive electrode, their initial specific capacity is higher, but because sulphur-after being dissolved in electrolyte, the micromolecule organic sulfur compound that produces during sulfide linkage fracture causes problems such as self discharge and capacity reduce rapidly, make the very fast decline of cycle performance of battery.This shows, be that the sulfuration macromolecule of skeleton has bigger superiority with the carbochain, and depolymerization does not take place when redox its main chain.(Composition based on a electronconducting polymer and its application to a positive active material for electrochemicalgenerators such as Perichaud, US Patent 4,664,991 1987) prepare polyacetylene with the polyvinyl chloride pyrolysis, again polyacetylene and elemental sulfur reaction are made (CH)
x/ S compound has higher specific capacity, but does not show charge-discharge performance as the disposable lithium-battery positive electrode.(Polycarbon sulfde Derivatives such as Armand, US Patent4,742,127,1998) be suspended in a kind of solvent with polytrifluorochloroethylene or polytetrafluoroethylene and lithium metal and react, filter under the product oxygen barrier, must vulcanize poly-carbon derivative (Polycarbon sulfide derivatives) (H with reaction of Salmon-Saxl
xCS
m)
n, wherein m and x are all between 0 and 1.The common still residual quite a large amount of fluorine that has of this class product, reason are that lithium betides the surface to the defluorination that gathers fluorohydrocarbon and be difficult to go deep into body inner mutually.CS such as Skotheim
2In solvent, generate poly-nitric sulfid (Polycarbon-Sulfide) (Electroactive high storagecapacity polycarbon-sulfide materials and electrolytic cells containing same.US Patent5 with the sodium metal reduction, 601,947,1997; US Patent 5,690,702,1997), again acetylene and elemental sulfur are reacted generation polyacetylene copolymerization sulphur (Polyacetylene-co-Polysulfur) (Electroactive high storagecapacity polyacetylene-co-Polysulfur materials and electrolytic cells containing same.USPatent 5 in the Sodamide liquid ammonia solution, 526,860,1996; 6,117,590,2000).This two classes electrode material all is a still mixture not really clearly of structure, uses a large amount of sodium metals in synthetic, and reaction condition requires harsh, and process is more numerous and diverse.Though their initial discharge capacity can reach more than the 800mAh/g, decay is very fast in the charge and discharge cycles.
Summary of the invention
The purpose of this invention is to provide a kind of new method for preparing carbyne polysulfide, and prepare high specific energy lithium primary battery with carbyne polysulfide as positive active material, this high specific energy lithium primary battery has very high discharge capacity; Prepare high specific energy lithium secondary battery, this high specific energy lithium secondary battery has the cycle performance that very high discharge capacity is become reconciled.
The carbyne polysulfide of naming among the present invention is meant that what have in the triple bond of carbyne that a key formed by the sulphur addition is a family macromolecule of skeleton with the conjugated double bond carbochain, and wherein carbon atom can link one or more sulphur atoms, and its structural formula is:
Sulphur atom in the formula on the carbon, can link to each other with another conjugated carbon chain forms crosslinked network structure (as shown in Equation 1), and the polynary ring (as shown in Equation 2) of formation more than five yuan or five yuan also can link to each other with a position carbon atom (or ortho position carbon).Exoergic or energy storage when sulphur-sulfide linkage fracture or bonding, thus can form new electrochemical energy storage system with lithium (or other metal).Structure is when m=1 or 1.5 in the formula 1, and its electrochemical equivalent is respectively 44 or 30, so theoretical specific capacity can reach 609 or 893mAh/g.As not considering cyclic reversibility (primary cell), can make m=3 or 4, then electrochemical equivalent reduces to 21.6 and 20 respectively, and theoretical specific capacity can be distinguished high to 1241 and 1340mAh/g.
The anode material of lithium battery that the present invention relates to is to make carbyne polysulfide by carbyne through baking.Be raw material with hydrogeneous polyalkenyl halides earlier, the hydrogen halides that removes wherein with alkali in organic solvent makes carbyne; Under inert gas shielding, be total to heat with elemental sulfur again and make carbyne polysulfide.Concrete preparation method is as follows:
1. be that raw material and alkali react in organic solvent with hydrogeneous polyalkenyl halides, reaction temperature is 0～100 ℃, and the time is 1～10h, and the hydrogen halides that removes wherein prepares carbyne.
With carbyne with after elemental sulfur evenly mixes with 1: 1～10 mol ratios, under nitrogen or argon shield,, make carbyne polysulfide at 50～400 ℃ of heating 0.5～10h.
The hydrogeneous polyalkenyl halides that the present invention relates to is Kynoar, poly-1,2-dichloroethene, Vingon and their copolymer and blend.
The organic solvent that the present invention relates to is ethanol, methyl alcohol, isopropyl alcohol, acetone, butanone, oxolane, N, dinethylformamide, N, N-dimethyl propylene acid amides, dimethyl sulfoxide (DMSO) etc. and mixed solvent thereof.
The used alkali of hydrogen halides that removes that the present invention relates to is KOH, NaOH, NH
3, DBU etc.
The present invention is a positive pole with the carbyne polysulfide material, and lithium metal, lithium alloy are negative pole, and the lithium of forming with organic bath once reaches secondary cell; Its discharge capacity reaches 700～1100mAh/g (in active material), after 50 circulations, keeps the capacity of 300～500mAh/g.
In the prepared lithium battery of the present invention, lithium primary battery can be with the carbyne polysulfide of extra-high-speed sulfur content (＞80%).
In the prepared lithium battery of the present invention, anodal preparation process is to take by weighing carbyne polysulfide 50～80mass% in proportion, conductive agent 30～10mass%, binding agent 20～10mass%, the adding proper amount of solvent stirs repeatedly and makes batch mixing evenly be paste after mixing, roll-in on flow collection sheet, treat solvent evaporates after, standby after the vacuumize.
In the positive electrode of the present invention's preparation, because active material has conductivity, so can use conductive agent less than other positive electrode; Conductive agent can be selected conductive carbon black, graphite powder etc. for use.Binding agent among the present invention can be selected PEO, PTFE, ethylene-propylene rubber, Kynoar etc. for use.
In the prepared lithium battery of the present invention, the negative pole available metal lithium of primary cell, the negative pole of secondary cell can be selected alloys such as the alloy of lithium metal, lithium and other alkali metal or alkaline-earth metal and Li/Al, Li/Si, Li/Pb, Li/Sn, Li/Sb, Li/Bi, Li/Zn, Li/Cd, Li/C for use.
In the prepared lithium battery of the present invention, electrolytical range of choice is liquid state, gel, solid-state electrolyte system.Liquid electrolyte can be selected for use and contain PC, DME, 1, a kind of organic solvent of 3-dioxolane, dimethoxy-ethane, ortho-xylene etc. or the mixture of several organic solvents.Supporting electrolyte can be lithium perchlorate, trifluoromethayl sulfonic acid lithium, lithium hexafluoro phosphate etc.
The carbyne polysulfide of the present invention preparation is the positive electrode of lithium battery, compares with other organic positive electrode that contains the S-S key, has that preparation technology is easy, with low cost, specific capacity is high, good conductivity, does not dissolve when discharging and recharging and advantage such as good reversibility.
The present invention is the lithium primary battery of positive electrode with the carbyne polysulfide of extra-high-speed sulfur content, makes positive electrode (as MnO with existing with other electroactive material
2, SO
2, SOCl
2) lithium primary battery compare, have with low cost, advantage such as specific energy is high and fail safe is good.
The present invention is the lithium secondary battery of positive electrode with the carbyne polysulfide, compares with existing various lithium ion batteries, has with low cost, advantage such as specific energy is high and fail safe is good.
Embodiment
Below prepare the embodiment of carbyne polysulfide and high energy storage lithium battery for the present invention.
Example 1
The preparation of carbyne: in the alcohol saturated solution (25mass.%) that 20g PVDC self-aggregate is slowly joined 800ml KOH and the mixed solution of 1200mL THF; room temperature reaction 1h under the nitrogen protection; after with the hydrochloric acid solution of 2M reactant liquor being neutralized to neutrality; the product filtered water is washed till no chloride ion; wash to filtrate with acetone more colourless, vacuum drying under the room temperature.Product is a black powder.
Example 2
The preparation of sulfuration carbyne: carbyne is mixed with 1: 5 (mol ratio) with sublimed sulfur, and ball milling 1 hour makes it even.Mixture speed with 10 ℃/min in tube furnace is heated to 150～300 ℃ of design temperatures, insulation 3h, logical nitrogen protection in the heat tracing process.
Example 3
300 ℃ of carbyne polysulfides that prepare down in the example 2 are mixed with 60%: 30%: 10% (mass.) with conductive carbon black and PEO, mixed solvent (the water: normal propyl alcohol=1: 4mass.) that adds entry and normal propyl alcohol, solids content is 15% in the batch mixing, stirring repeatedly makes batch mixing evenly be paste, roller coat is on aluminum foil current collector then, placed under the room temperature 8 hours, and treated after the solvent evaporates again in following 60 ℃ of bakings of vacuum condition 10 hours standby.Prepared anode pole piece coating layer thickness is 40～45 μ m.
Example 4
Pole piece with making in the example 3 is a positive pole, is negative pole with Li, and barrier film is selected polypropylene screen for use, and electrolyte is the LiCF of 1mol/L
3SO
3Solution, solvent be 50% 1,3-dioxolane, 35% diethylene glycol dimethyl ether, 15% dimethoxy-ethane.(humidity is less than 1%) is assembled into battery in glove box.The open circuit voltage of battery is 3.2 volts.
Example 5
The battery of making in the example 4 is carried out the charge-discharge performance test at ambient temperature, and deboost is 3.0V to 1.5V, at 2.1V a very long discharge platform is arranged.When charging and discharging currents density is 0.08mA/cm
2The time, the head of battery is put capacity and is reached 1082mAh/g; When charging and discharging currents density is 0.40mAh/cm
2The time, it is 773mAh/g that the head of battery is put capacity, after 50 circulations, leaves the specific capacity of 350mAh/g.
Claims (7)
1. an anode material of lithium battery is characterized in that making carbyne polysulfide by carbyne through baking; Be raw material with hydrogeneous polyalkenyl halides earlier, the hydrogen halides that removes wherein with alkali in organic solvent makes carbyne, is total to heat with elemental sulfur under inert gas shielding again and makes carbyne polysulfide.
2. the preparation method of carbyne polysulfide according to claim 1 is characterized in that hydrogeneous polyalkenyl halides is Kynoar, poly-1,2-dichloroethene, Vingon and their copolymer and blend.
3. the preparation method of carbyne polysulfide according to claim 1, it is characterized in that organic solvent is ethanol, methyl alcohol, isopropyl alcohol, acetone, butanone, oxolane, N, dinethylformamide, N, N-dimethyl propylene acid amides, dimethyl sulfoxide (DMSO) etc. and mixed solvent thereof.
4. the preparation method of carbyne polysulfide according to claim 1, it is characterized in that removing the used alkali of hydrogen halides is KOH, NaOH, NH
3, DBU etc.
5. the preparation method of carbyne polysulfide according to claim 1 is characterized in that hydrogeneous polyalkenyl halides and alkali react in organic solvent, and temperature is 0～100 ℃, and the time is 1～10h, removes hydrogen halides and makes carbyne.
6. the preparation method of carbyne polysulfide according to claim 1, it is characterized in that with carbyne and elemental sulfur with 1: 1～10 mixed in molar ratio after, at nitrogen or/and under the argon shield,, make carbyne polysulfide in 50～400 ℃ of heating 0.5～10h.
7. anode material of lithium battery according to claim 1 is characterized in that with the carbyne polysulfide being positive electrode, is negative material with lithium or lithium alloy, form lithium battery with organic bath, discharge capacity reaches 700～1100mAh/g, after 50 circulations, keeps the capacity of 300～500mAh/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100376976A CN1691381A (en) | 2004-04-29 | 2004-04-29 | Preparation of lithium battery anode material carbon polysulfide alkyne |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2004100376976A CN1691381A (en) | 2004-04-29 | 2004-04-29 | Preparation of lithium battery anode material carbon polysulfide alkyne |
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| CN1691381A true CN1691381A (en) | 2005-11-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384911C (en) * | 2006-05-26 | 2008-04-30 | 武汉大学 | Aromatic acid anhydride sulfurized polymer |
| CN106159273A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of material with carbon element preparation method for lithium-sulfur cell with high reaction activity |
| CN106159221A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of nano-sized carbon sulfur composite for lithium-sulfur cell |
-
2004
- 2004-04-29 CN CNA2004100376976A patent/CN1691381A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384911C (en) * | 2006-05-26 | 2008-04-30 | 武汉大学 | Aromatic acid anhydride sulfurized polymer |
| CN106159273A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of material with carbon element preparation method for lithium-sulfur cell with high reaction activity |
| CN106159221A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of nano-sized carbon sulfur composite for lithium-sulfur cell |
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