CN102127828A - Porous nano carbon fiber material, lithium battery cathode material and cathode plate - Google Patents
Porous nano carbon fiber material, lithium battery cathode material and cathode plate Download PDFInfo
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- CN102127828A CN102127828A CN201110027735XA CN201110027735A CN102127828A CN 102127828 A CN102127828 A CN 102127828A CN 201110027735X A CN201110027735X A CN 201110027735XA CN 201110027735 A CN201110027735 A CN 201110027735A CN 102127828 A CN102127828 A CN 102127828A
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract 25
- 239000004917 carbon fiber Substances 0.000 title claims abstract 25
- 239000010406 cathode material Substances 0.000 title claims 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000006230 acetylene black Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 239000011888 foil Substances 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001523 electrospinning Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- -1 poly(acrylonitrile-methyl methacrylate) Polymers 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 229920002959 polymer blend Polymers 0.000 claims 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- 235000011167 hydrochloric acid Nutrition 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 claims 1
- 239000004626 polylactic acid Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims 1
- 229920003048 styrene butadiene rubber Polymers 0.000 claims 1
- 238000000859 sublimation Methods 0.000 claims 1
- 230000008022 sublimation Effects 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002134 carbon nanofiber Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 72
- 238000002360 preparation method Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000005864 Sulphur Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 244000208060 Lawsonia inermis Species 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种多孔纳米碳纤维材料，以及由该多孔纳米碳纤维材料制备而得的锂电池单质硫/多孔纳米碳纤维复合正极材料和正极片。一种锂电池单质硫/多孔纳米碳纤维复合正极片，由以下方法制备得到：(1)将权利要求3所述的锂电池单质硫/多孔纳米碳纤维复合正极材料、乙炔黑和粘接剂混合，搅拌均匀，得到混合物；(2)向步骤(1)得到的混合物中加入N-甲基吡咯烷酮溶液，调成膏状刮涂于集流体表面涂碳的铝箔上，干燥后即得到单质硫/多孔纳米碳纤维复合正极片。利用本发明正极片制作而成的锂硫电池，其循环性能得到较大提高。The invention discloses a porous nano-carbon fiber material, and a lithium battery elemental sulfur/porous nano-carbon fiber composite positive electrode material and positive electrode sheet prepared from the porous nano-carbon fiber material. A lithium battery elemental sulfur/porous nano-carbon fiber composite positive electrode sheet, prepared by the following method: (1) mixing the lithium battery elemental sulfur/porous nano-carbon fiber composite positive electrode material according to claim 3, acetylene black and a binder, Stir evenly to obtain a mixture; (2) Add N-methylpyrrolidone solution to the mixture obtained in step (1), adjust it into a paste and scrape it on the aluminum foil coated with carbon on the surface of the current collector, and obtain elemental sulfur/porous after drying Carbon nanofiber composite cathode sheet. The cycle performance of the lithium-sulfur battery made by using the positive electrode sheet of the invention is greatly improved.
Description
Technical field
The present invention relates to electrochemical field, be specifically related to a kind of material that is used to prepare lithium battery, particularly a kind of porous filamentous nanocarbon material, lithium battery elemental sulfur/porous filamentous nanocarbon composite positive pole and the positive plate that forms by this porous filamentous nanocarbon material preparation.
Background technology
Energy shortage and environmental pollution are two hang-ups that the world today pays close attention to the most.Application is that the energy shortage that transport facility produced and the problem of environmental pollution of power is especially outstanding with the fuel oil, solution at a specified future date is to use Hydrogen Energy, but economy and technical merit assessment result show, the solution that Hydrogen Energy is used the many infrastructure problems that relate to needs time, and the midium or long term is interior to be that the pure power or the hybrid power energy are the inevitable choices that solves energy shortage and environmental pollution with secondary cell.
Lithium ion battery because have that the close height of energy, self discharge are little, memory-less effect, operating temperature range are wide, have extended cycle life and advantage such as environmentally friendly, being the best new green environment protection high energy secondary cell of present combination property, is one of optimal electrical source of power.But the commercialization lithium ion battery is subjected to its positive electrode transition metal oxide such as LiCoO at present
2, LiMnO
2And LiFePO
4Etc. the restriction of relatively low theoretical specific capacity, its height ratio capacity can only reach 100～130Wh/kg, is difficult to satisfy the requirement of electrokinetic cell needs high-capacity electrode material.
The theoretical specific capacity of elemental sulfur is 1672mAh/g, is assembled into battery with lithium, and theoretical specific energy can reach 2600Wh/kg, meets the requirement of electric automobile to battery, also meets the requirement of portable type electronic product to battery " light, thin, little "; And sulphur has wide material sources (cost is low), nontoxic characteristics such as (pollution-free).Advantages such as therefore, the sulfur-bearing composite positive pole is with its high power capacity, low cost, and hypotoxicity, cycle performance are better become and have one of positive electrode of development prospect most at present, and being has exploitation to be worth and the secondary dynamic lithium battery positive electrode of application prospect.But capacity attenuation is rapidly the greatest problem that present sulphur positive electrode runs in lithium battery applications, and reason is that their electronic and ionic insulation and material or embedding lithium product is dissolved in organic solvent.Therefore, improve the sulphur positive electrode electrical conductivity, reduce or the solvent solubility that overcomes active sulfur is the key of dealing with problems.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of porous filamentous nanocarbon material with not enough.
Another object of the present invention is to provide a kind of lithium battery elemental sulfur/porous filamentous nanocarbon composite positive pole that forms by above-mentioned porous filamentous nanocarbon material preparation.
A further object of the present invention be to provide a kind of that be prepared from by above-mentioned lithium battery elemental sulfur/porous filamentous nanocarbon composite positive pole, have a lithium battery anode sheet of cyclical stability preferably.
Purpose of the present invention is achieved through the following technical solutions:
A kind of porous filamentous nanocarbon material is prepared by following method:
(1) blend polymer or copolymer are dissolved in the solvent, form homogeneous polymer solution;
(2) polymer solution is used for the electric field spinning, obtaining diameter is that tens nanometers arrive several microns fiber; Polymer solution is under the effect of high-voltage DC power supply, can overcome surface tension, form and spray thread, in course of injection, solvent constantly volatilizees, the unstability of jet and the effect of electrostatic force constantly are stretched jet, and jet division phenomenon takes place sometimes, and finally obtaining diameter on gatherer is that tens nanometers arrive several microns fiber;
(3) the electrospinning silk that step (2) is obtained heating, pre-oxidation 2～4h under 160～280 ℃; The electrospinning silk carries out heat carbonization 1～3h after the pre-oxidation, obtains the porous filamentous nanocarbon material.
The described blend polymer of step (1) is a kind of in the following combination:
1. the mixture of polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA), both mass ratioes are 9: 1～1: 1;
2. the mixture of polyacrylonitrile (PAN) and polystyrene (PS), both mass ratioes are 9: 1～1: 1;
3. the mixture of polyacrylonitrile (PAN) and Poly-L-lactic acid (PLLA), both mass ratioes are 9: 1～1: 1;
A kind of among poly-(acrylonitrile-methyl methacrylate) P (AN-MMA), poly-(acrylonitrile-styrene) P (AN-St), poly-(acrylonitrile-D-lactic acid) P (AN-LLA) or poly-(acrylonitrile-vinyl acetate) P (AN-VAc) of the described copolymer of step (1); The mol ratio of two kinds of monomers is 9: 1～1: 1 in the described copolymer;
The described solvent of step (1) is N, a kind of in dinethylformamide (DMF), oxolane (THF) or the dimethyl sulfoxide (DMSO) (DMSO); The mass fraction of described polymer solution is 8～10%;
The voltage of the described electric field spinning of step (2) is 10～20kV, and the distance between capillary end and the gatherer is 10cm;
The pre-oxidation of the described electrospinning silk of step (3), its heating rate is 10 ℃/min;
The described electrospinning silk of step (3) high temperature cabonization is to be protective gas with nitrogen; The temperature of described carbonization is 600～1200 ℃.
Resulting porous filamentous nanocarbon material is that length is that the microporous high-specific surface area active carbon material that the aperture is 2～10nm is contained in 2～10 μ m, diameter 50～200nm, inside.
A kind of lithium battery elemental sulfur/porous filamentous nanocarbon composite positive pole is prepared by following method:
(1) gets the sublimed sulfur powder, join in the sodium sulfide solution and react, under 20～40 ℃, be stirred to the sulphur powder and all dissolve, obtain henna sodium polysulfide (Na
2S
x) solution, filter, get filtrate;
(2) sodium polysulfide solution and above-mentioned porous filamentous nanocarbon material are joined simultaneously contain in the surfactant solution, ultrasonic agitation obtained yellow solution A in 40～60 minutes;
(3) add surfactant in the acid solution and obtain solution B;
(4) solution A is slowly splashed in the solution B, dropwise the back and continue to stir 30～60 minutes, the gained mixed liquor is filtered, get precipitation; With washing of precipitate, drying, obtain elemental sulfur/porous filamentous nanocarbon composite positive pole.
The mol ratio of described sulphur powder of step (1) and vulcanized sodium is 2: 1～5: 1;
The concentration of the described surfactant solution of step (2) is 4～8mM/L, and surfactant solution is regulated it more than pH value to 8 with the NaOH solution of 0.1～0.2mol/L before use;
The concentration of the described acid solution of step (3) is 2mol/L; The surfactant that contains 4～8mM/L in the described solution B;
Step (4) is described to splash into solution A in the solution B, drips speed control built in 30～40/min; Described is respectively to wash 3 times with acetone and deionized water with washing of precipitate; The described drying that will precipitate is following dry 24～36 hours at 40～60 ℃;
The mass ratio of described sublimed sulfur powder and porous filamentous nanocarbon is 2: 1～9: 1;
Described surfactant is a kind of in softex kw (CTAB), sodium cetanesulfonate (SDS), neopelex (SDBS) or the polyethylene glycol-400 (PEG-400);
The acid of described acid solution is formic acid (HCOOH), oxalic acid (H
2C
2O
4) or hydrochloric acid (HCl) in a kind of;
In resulting elemental sulfur/porous filamentous nanocarbon composite positive pole, the mass ratio of sulphur and porous filamentous nanocarbon is 5: 5～9: 1.
A kind of lithium battery elemental sulfur/porous filamentous nanocarbon anode composite sheet is to be prepared by following method:
(1) above-mentioned elemental sulfur/porous filamentous nanocarbon composite positive pole, acetylene black and bonding agent are mixed, stir, obtain mixture;
(2) add N-Methyl pyrrolidone (NMP) solution in the mixture that step (1) obtains, furnishing paste blade coating is coated with in collection liquid surface on the aluminium foil of carbon, promptly obtains elemental sulfur/porous filamentous nanocarbon anode composite sheet after the drying.
Elemental sulfur in the described mixture of step (1)/porous filamentous nanocarbon composite positive pole content is 60%～90%, and acetylene black content is 0～30%, and bonding agent content is 6%～10%, and described percentage is mass percent;
In the step (2), coating layer thickness is 50～100 μ m;
Described binding agent is a kind of in the following combination:
1. Kynoar (PVDF);
2. polytetrafluoroethylene (PTFE);
3. polyethylene glycol oxide (PEO);
4. the mixture of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR), both mass ratioes are 1: 2.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention adopts the electrospinning weave to prepare the porous filamentous nanocarbon material, and is simple to operate, and the aperture is controlled and be evenly distributed; This material has high-specific surface area and high conductivity, has associativity closely with nano active sulphur, helps improving the utilization rate of active sulfur, reduces or overcome the solvent solubility of active sulfur.
(2) the present invention adopts the chemical codeposition legal system to be equipped with elemental sulfur/porous filamentous nanocarbon composite positive pole, because high conductivity high-ratio surface active nano carbon fibre material not only has good electrical conductivity but also can keep the electrode material stability of structure; Thereby the good stability at the lithium ion cell electrode interface that obtains; The adding of porous filamentous nanocarbon simultaneously makes electrode slice have splendid crosslinked network structure, and for the migration of lithium ion provides a passage easily, the ionic conductivity of sulfur electrode improves greatly, thereby the cycle performance of lithium-sulfur cell also obtains bigger raising.
(3) technology of the present invention is simple, and is not harsh to operation and environmental requirement, for technology production provides simple and easy to do condition.
Description of drawings
Fig. 1 be the lithium-sulfur cell made with the positive plate of embodiment 7 under 25 ℃ of 40mA/g first with the charging and discharging curve figure second time;
Fig. 2 is the discharge cycles life diagram of lithium-sulfur cell under 25 ℃ of 40mA/g made from the positive plate of embodiment 7.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
The preparation of embodiment 1 high surface carbon nano-fiber material
With mass percent is 8% polyacrylonitrile (PAN)/polymethyl methacrylate (PMMA) (7: 3, mass ratio) powder dissolution is in mass percent is 92% N-N dimethyl formamide (DMF), powerfully down stirs 24h and obtains homogeneous polymer solution at 60 ℃.This solution is to carry out the electric field spinning under the effect of 20kV high-voltage DC power supply at voltage.The above-mentioned electrospinning silk that obtains carries out pre-oxidation 2h at 280 ℃; 10 ℃/min of control heating rate; pre-oxidation electrospinning silk is that protective gas carries out high temperature cabonization with nitrogen in tube furnace; at 1200 ℃ of following carbonization 1h, obtain the porous filamentous nanocarbon material at last: the about 10nm multi-cellular structure in aperture is contained in the about 8 μ m of length, diameter 200nm, inside.
The preparation of embodiment 2 high surface carbon nano-fiber materials
With mass percent poly-(acrylonitrile-styrene) P (AN-St) (AN: St=8: 2 of 10%, mol ratio) powder dissolution is in mass percent is 90% N-N dimethyl formamide (DMF), powerfully down stirs 24h and obtains homogeneous polymer solution at 60 ℃.This solution is to carry out the electric field spinning under the effect of 10kV high-voltage DC power supply at voltage.The above-mentioned electrospinning silk that obtains carries out pre-oxidation 4h at 160 ℃; 10 ℃/min of control heating rate; pre-oxidation electrospinning silk is that protective gas carries out high temperature cabonization with nitrogen in tube furnace; at 600 ℃ of following carbonization 3h, obtain the porous filamentous nanocarbon material at last: the about 8nm multi-cellular structure in aperture is contained in the about 6 μ m of length, diameter 150nm, inside.
The preparation of embodiment 3 lithium batteries elemental sulfur/porous filamentous nanocarbon composite positive pole
Get the porous filamentous nanocarbon material preparation elemental sulfur/porous filamentous nanocarbon composite positive pole of example 1.
Get 1g vulcanized sodium and be dissolved in the 20mL deionized water, make sodium sulfide solution.With 1.23g sublimed sulfur powder, join in the above-mentioned sodium sulfide solution and react, 25 ℃ are stirred down 3h and all dissolve to the sulphur powder, obtain henna sodium polysulfide (Na
2S
x) solution, and filter.0.182g surfactant softex kw (CTAB) is dissolved in the 100mL deionized water, and transfer to pH＞8 with the NaOH solution of 0.1mol/L, sodium polysulfide solution and 0.3g porous filamentous nanocarbon material after filtering are joined in the deionized water that contains Surfactant CTAB simultaneously, and ultrasonic agitation obtained yellow solution (A) in 60 minutes then.
Formic acid (HCOOH) solution of preparation 100mL 2mol/L, and add 0.182gCTAB, shake up then and obtain solution (B).With separatory funnel solution (A) slowly is added dropwise in the solution (B), speed is controlled at 30～40/min, dropwising the back continues to stir 60 minutes, the gained mixed liquor is filtered, respectively wash 3 times with acetone and deionized water, drying is 36 hours under 50 ℃, obtains elemental sulfur/porous filamentous nanocarbon composite positive pole at last, and the content of sulphur is 78.8%.
The preparation of embodiment 4 lithium batteries elemental sulfur/porous filamentous nanocarbon composite positive pole
Get the porous filamentous nanocarbon material preparation elemental sulfur/porous filamentous nanocarbon composite positive pole of example 1.
Get 0.30g vulcanized sodium and be dissolved in the 20mL deionized water, make sodium sulfide solution.With 0.37g sublimed sulfur powder, join in the above-mentioned sodium sulfide solution and react, 20 ℃ are stirred down 3h and all dissolve to the sulphur powder, obtain henna sodium polysulfide (Na
2S
x) solution, and filter.0.182g surfactant softex kw (CTAB) is dissolved in the 100mL deionized water, and transfer to pH＞8 with the NaOH solution of 0.1mol/L, sodium polysulfide solution and 0.2g porous filamentous nanocarbon material after filtering are joined in the deionized water that contains Surfactant CTAB simultaneously, and ultrasonic agitation obtained yellow solution (A) in 60 minutes then.
Oxalic acid (the H of preparation 100mL 2mol/L
2C
2O
4) solution, and add 0.182gCTAB, shake up then and obtain solution (B).With separatory funnel solution (A) slowly is added dropwise in the solution (B), speed is controlled at 30～40/min, dropwising the back continues to stir 30 minutes, the gained mixed liquor is filtered, respectively wash 3 times with acetone and deionized water, drying is 36 hours under 50 ℃, obtains elemental sulfur/porous filamentous nanocarbon composite positive pole at last, and the content of sulphur is 65%.
The preparation of embodiment 5 lithium batteries elemental sulfur/porous filamentous nanocarbon composite positive pole
Get the porous filamentous nanocarbon material preparation elemental sulfur/porous filamentous nanocarbon composite positive pole of example 2.
Get 0.73g vulcanized sodium and be dissolved in the 20mL deionized water, make sodium sulfide solution.With 0.9g sublimed sulfur powder, join in the above-mentioned sodium sulfide solution and react, stir down 3h at 30 ℃ and all dissolve to the sulphur powder, obtain henna sodium polysulfide (Na
2S
x) solution, filtrate for later use.1g surfactant polyethylene-400 (PEG) is dissolved in the 100mL deionized water, and transfer to pH＞8 with the NaOH solution of 0.1mol/L, sodium polysulfide solution and 0.1g porous filamentous nanocarbon material after filtering are joined in the deionized water that contains Surfactant CTAB simultaneously, and ultrasonic agitation obtained yellow solution (A) in 60 minutes then.
Oxalic acid (the H of preparation 100mL 2mol/L
2C
2O
4) solution, and add 1g PEG, shake up then and obtain solution (B).With separatory funnel solution (A) slowly is added dropwise in the solution (B), speed is controlled at 30～40/min, dropwising the back continues to stir 40 minutes, the gained mixed liquor is filtered, respectively wash 3 times with acetone and deionized water, drying is 36 hours under 50 ℃, obtains elemental sulfur/porous filamentous nanocarbon composite positive pole at last, and the content of sulphur is 89.6%.
The preparation of embodiment 6 lithium batteries elemental sulfur/porous filamentous nanocarbon composite positive pole
Get the porous filamentous nanocarbon material preparation elemental sulfur/porous filamentous nanocarbon composite positive pole of example 2.
Get 0.23g vulcanized sodium and be dissolved in the 20mL deionized water, make sodium sulfide solution.With 0.28g sublimed sulfur powder, join in the above-mentioned sodium sulfide solution and react, stir down 3h at 40 ℃ and all dissolve to the sulphur powder, obtain henna sodium polysulfide (Na
2S
x) solution, and filter.0.182gCTAB is dissolved in the 100mL deionized water, and transfer to pH＞8 with the NaOH solution of 0.1mol/L, sodium polysulfide solution and 0.1g porous filamentous nanocarbon material after filtering are joined in the deionized water that contains Surfactant CTAB simultaneously, and ultrasonic agitation obtained yellow solution (A) in 60 minutes then.
Formic acid (HCOOH) solution of preparation 100mL 2mol/L, and add 0.182gCTAB, shake up then and obtain solution (B).With separatory funnel solution (A) slowly is added dropwise in the solution (B), speed is controlled at 30～40/min, dropwising the back continues to stir 60 minutes, the gained mixed liquor is filtered, respectively wash 3 times with acetone and deionized water, drying is 36 hours under 50 ℃, obtains elemental sulfur/porous filamentous nanocarbon composite positive pole at last, and the content of sulphur is 75.2%.
The preparation of embodiment 7 lithium batteries elemental sulfur/porous filamentous nanocarbon anode composite sheet
Elemental sulfur/porous filamentous nanocarbon composite positive pole of getting example 3 prepares elemental sulfur/porous filamentous nanocarbon anode composite sheet.
0.7g elemental sulfur/porous filamentous nanocarbon composite positive pole, 0.24g acetylene black are mixed with the different quality ratio with the 0.06gPVDF adhesive, add nmp solution, furnishing paste blade coating is coated with on the aluminium foil of carbon in collection liquid surface, coating layer thickness is 50 μ m, promptly obtains elemental sulfur/porous filamentous nanocarbon anode composite sheet after the drying.
Above-mentioned elemental sulfur/porous filamentous nanocarbon anode composite sheet, PE/PP barrier film and lithium sheet negative material are assembled into 2032 button cells, inject electrolyte (1mol/kg LiTFSI+PYR
14TFSI+PEGDME, PYR
14TFSI: the PEGDME mass ratio is 1: 1), leave standstill after the sealing and be used for the test battery charge-discharge performance in 24 hours.The lithium-sulfur cell charge-discharge performance as depicted in figs. 1 and 2, battery discharges first and reaches 1109mAh/g as can be seen from Figure 1, and has charge and discharge platform more stably; Battery has cyclical stability preferably as can be seen from Figure 2, and 30 times the circulation back keeps more than the 800mAh/g.
The preparation of embodiment 8 lithium batteries elemental sulfur/porous filamentous nanocarbon anode composite sheet
Elemental sulfur/porous filamentous nanocarbon composite positive pole of getting example 4 prepares elemental sulfur/porous filamentous nanocarbon anode composite sheet.
0.6g elemental sulfur/porous filamentous nanocarbon composite positive pole, 0.3g acetylene black and 0.1g (CMC+SBR) (both mass ratioes are 1: 2) adhesive are mixed, add nmp solution, furnishing paste blade coating is coated with on the aluminium foil of carbon in collection liquid surface, coating layer thickness is 75 μ m, promptly obtains elemental sulfur/porous filamentous nanocarbon anode composite sheet after the drying.
Above-mentioned elemental sulfur/porous filamentous nanocarbon anode composite sheet, PE/PP barrier film and lithium sheet negative material are assembled into 2032 button cells, inject electrolyte (1mol/kg LiTFSI+PYR
14TFSI+PEGDME, PYR
14TFSI: the PEGDME mass ratio is 1: 1), leave standstill after the sealing and be used for the test battery charge-discharge performance in 24 hours.Lithium-sulfur cell discharges first and reaches 1209mAh/g, and 30 times the circulation back keeps 760mAh/g.
The preparation of embodiment 9 lithium batteries elemental sulfur/porous filamentous nanocarbon anode composite sheet
Elemental sulfur/porous filamentous nanocarbon composite positive pole of getting example 5 prepares elemental sulfur/porous filamentous nanocarbon anode composite sheet.
0.9g elemental sulfur/porous filamentous nanocarbon composite positive pole and 0.1gPVDF adhesive are mixed with the different quality ratio, add nmp solution, furnishing paste blade coating is coated with on the aluminium foil of carbon in collection liquid surface, coating layer thickness is 100 μ m, promptly obtains elemental sulfur/porous filamentous nanocarbon anode composite sheet after the drying.
Above-mentioned elemental sulfur/porous filamentous nanocarbon anode composite sheet, PE/PP barrier film and lithium sheet negative material are assembled into 2032 button cells, inject electrolyte (1mol/kg LiTFSI+PYR
14TFSI+PEGDME, PYR
14TFSI: the PEGDME mass ratio is 1: 1), leave standstill after the sealing and be used for the test battery charge-discharge performance in 24 hours.Lithium-sulfur cell discharges first and reaches 1301mAh/g, and 30 times the circulation back keeps 590mAh/g.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
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| C06 | Publication | ||
| PB01 | Publication | ||
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