CN103435105B - A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application - Google Patents
A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application Download PDFInfo
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- CN103435105B CN103435105B CN201310341332.1A CN201310341332A CN103435105B CN 103435105 B CN103435105 B CN 103435105B CN 201310341332 A CN201310341332 A CN 201310341332A CN 103435105 B CN103435105 B CN 103435105B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 110
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010406 cathode material Substances 0.000 title claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 131
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000002131 composite material Substances 0.000 claims abstract description 66
- 239000011159 matrix material Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000007791 liquid phase Substances 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 238000005507 spraying Methods 0.000 claims abstract description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- 238000005336 cracking Methods 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000012298 atmosphere Substances 0.000 claims description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000003570 air Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 239000005639 Lauric acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000006902 nitrogenation reaction Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 239000007921 spray Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 29
- 238000003860 storage Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 20
- 230000004087 circulation Effects 0.000 description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 16
- 230000002441 reversible effect Effects 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 150000001722 carbon compounds Chemical class 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- 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 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000004452 microanalysis Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation method of iron oxide/carbon composite material, step is as follows: 1) with water-soluble molysite for source of iron, with Water Soluble Organic Carbon source for carbon source, molysite aqueous solution and ammoniacal liquor and organic carbon source are mixed, obtain liquid phase mixture; 2) adopt the method for spraying dry, lyophilize or cracking of spraying to form powder presoma to this liquid phase mixture, then this presoma is calcined, be prepared into iron oxide/carbon composite material; Or directly spraying cracking is carried out to this mixing solutions, be prepared into iron oxide/carbon composite material.The invention provides a kind of method preparing iron oxide/carbon composite material, the method production efficiency is high, is applicable to large-scale production; The present invention improves the utilising efficiency of matrix material; Iron oxide/carbon composite material provided by the invention, as lithium ion battery negative material, has the lithium storage content being several times as much as business carbon negative pole material.
Description
Technical field
The invention belongs to field of energy source materials.Be specifically related to a kind of Novel cathode material for lithium ion battery and preparation method thereof, use negative pole and the lithium ion battery thereof of this material.
Technical background
Along with modern society is to the increase day by day of energy demand and the raising day by day to environmental protection requirement; the continuous exhaustion of tradition fossil resources increasingly sharpens to the contradiction of the pollution of environment and the development of modern society with it; lithium ion battery is as the green secondary power supply grown up over a kind of nearly 20 years; because its energy density is high, have extended cycle life, self-discharge is little, memory-less effect, advantages of environment protection, be used widely in the power supply of the small portable movable electrical appliances such as computer, mobile telephone, MP3.The deposit of current electromobile, hybrid-electric car, electric bicycle, sun power and wind energy and conversion, the demand of power tool to the high-energy-density of safety, environmental protection and the secondary power supply of high power density increase day by day, and wherein lithium ion battery has the potentiality meeting its application requiring.The lithium ion battery negative material mainly graphitic carbon material of unique large-scale commercial at present, but its theoretical capacity is about 372mAh/g, can not meet the requirement of high power density, high-energy-density.Graphite carbon not only theoretical capacity is low, and its weight density only has 2.2 ~ 2.4g/cm
3, this reduces the volume capacity of battery to a great extent, particularly unfavorable to the volume density of large-sized battery.Thus, many countries have all dropped into a large amount of negative material of energy and financial resources to lithium ion battery and conduct extensive research and develop in recent years.
The oxide compound of the transition metal such as Ti, Fe, Cu, Co and Ni has the characteristic of heavy body as lithium ion battery negative material, have the possibility of potential alternative graphitic carbon negative electrode material.In electrochemistry removal lithium embedded process, following reaction is there is in transition metal oxide as lithium ion battery negative material:
In formula, M is transition metal oxide.Transition metal oxide has larger volumetric expansion in embedding lithium process, and make material generation efflorescence, lose effective electrical contact, the cyclical stability of material is poor.In addition, the Li owing to generating in embedding lithium process first
2irreversible and the irreversible capacity that formed of solid electrolyte film (SEI film) owing to being formed at the negative material ubiquitous electrode materials in surface and electrolytic solution reaction of O part, makes transition metal oxide also ubiquity irreversible high shortcoming first.In transition metal oxide negative material, ferriferous oxide due to its capacity high, cheap, wide material sources, advantages such as safety non-toxic and easily storage and receiving much attention.As Fe
2o
3and Fe
3o
4theoretical capacity as lithium ion battery negative material reaches 1005mAh/g and 926mAh/g respectively, is about 3 times of graphite cathode material.In addition, the weight density of ferriferous oxide is about 5.2g/cm
3, be about 2.5 times of graphite, thus ferriferous oxide has higher volume and capacity ratio as lithium ion battery negative material, and this has obvious advantage for its commercialization practical application.Described in indulging above, ferriferous oxide negative material is a kind of lithium ion battery negative material of new generation having development and application potential.But also need the subject matter solved to be keeping material high capacity characteristics while, improve the cycle performance of material and reduce the irreversible capacity first of material.
Summary of the invention
In order to solve the problems of the technologies described above, first object of the present invention is to provide a kind of preparation method of ferriferous oxide/carbon composition lithium ion battery cathode material.Ferriferous oxide/carbon is once formed simultaneously, and the method technique is simple, and raw material sources is abundant, with low cost, is applicable to large-scale production.Second object of the present invention is to provide ferriferous oxide/carbon compound cathode materials prepared by aforesaid method.In this material, ferriferous oxide is mainly embedded in carbon base body, and both contact closely.Ferriferous oxide maintains the characteristic of its heavy body, the introducing of carbon not only effectively improves the electronic conductivity between iron oxide particle, also effectively cushion the volume change of ferriferous oxide in removal lithium embedded process, reduced the efflorescence of iron oxide particle, effectively improve the utilization ratio of material.This iron oxide/carbon composite material has that charge/discharge capacity is high, the advantage of good cycle.3rd object of the present invention is to provide the lithium ion battery negative using this matrix material.4th object of the present invention is to provide the lithium ion battery using this negative pole.
In order to realize first above-mentioned object, present invention employs following technical scheme:
A preparation method for iron oxide/carbon composite material, the method comprises the following steps:
1) with water-soluble molysite for source of iron,
with Water Soluble Organic Carbon source for carbon source, molysite aqueous solution and ammoniacal liquor and organic carbon source are mixed, obtain liquid phase mixture;
2) adopt the method for spraying dry, lyophilize or cracking of spraying to form powder presoma to this liquid phase mixture, then this presoma is calcined, be prepared into iron oxide/carbon composite material; Or directly spraying cracking is carried out to this mixing solutions, be prepared into iron oxide/carbon composite material; In described iron oxide/carbon composite material, the content of carbon is 5 ~ 70wt% of matrix material mass percent, and the content of preferred carbon is 20 ~ 60% of matrix material mass percent, and described ferriferous oxide is amorphous compound, FeO, Fe of iron and oxygen
3o
4, Fe
2o
3in one or more.
As preferably, described water-soluble molysite is one or more mixing in iron trichloride, iron protochloride, ironic oxalate, iron nitrate, ferric sulfate and ferrous sulfate and their crystalline hydrate, is preferably lower-cost iron trichloride or its crystalline hydrate.
As preferably, described
water Soluble Organic Carbon sourcefor one or more in citric acid, lauric acid, sucrose, glucose and polyvinyl alcohol.
As preferably, described water-soluble molysite and the mol ratio of ammoniacal liquor are 1:(0.2 ~ 20), be preferably 1:(1 ~ 5); Molysite with
water-solublethe mol ratio of organic carbon source is 1:(0.2 ~ 8), be preferably 1:(0.5 ~ 5); The volumetric molar concentration of water-soluble molysite is the saturated volumetric molar concentration of 0.5 mol/L ~ molysite, and the concentration of ammoniacal liquor is 3 ~ 15 mol/L.
As preferably, described liquid phase mixture adopts spraying dry to prepare powder presoma, and drying temperature is 100 ~ 500 DEG C, preferably 150 ~ 400 DEG C; Dry atmosphere can adopt the mixed gas of air, nitrogen, argon gas or more one or more gases, is preferably air; Then, calcine the powder presoma that drying obtains, calcining temperature is 300 ~ 900 DEG C, is preferably 350 ~ 700 DEG C; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or more one or more gases; The time of calcining is 0.5 ~ 6 hour, is preferably 1 ~ 4 hour.
As preferably, described liquid phase mixture is under the mixed gas of one or more gases of air, nitrogen, argon gas or more, and cracking of spraying at 300 ~ 900 DEG C, directly forms iron oxide/carbon composite material; As preferably, spraying cracking temperature is 350 ~ 800 DEG C, and cracking atmosphere adopts air.
As preferably, described liquid phase mixture is sprayed at the mixed gas of one or more gases of air, nitrogen, argon gas or more and is cracked into powder presoma at 100 ~ 500 DEG C, and then at 300 ~ 900 DEG C, calcine 0.5 ~ 6 hour in an inert atmosphere, form iron oxide/carbon composite material; Inert atmosphere is the mixed gas of nitrogen, argon gas or nitrogen and argon gas; As preferably, cracking atmosphere adopts air; As preferably, calcination atmosphere adopts nitrogen, and calcination time is 1 ~ 4 hour.
As preferably, described liquid phase mixture adopts lyophilize to prepare powder presoma, drying temperature be-10 ~-70 DEG C, preferably-20 ~-50 DEG C, and adopts dynamic vacuum; Then, calcine the powder presoma that drying obtains, calcining temperature is 300 ~ 900 DEG C, is preferably 350 ~ 700 DEG C; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or more one or more gases; The time of calcining is 0.5 ~ 6 hour, is preferably 1 ~ 4 hour.
In order to realize second above-mentioned object, present invention employs following technical scheme:
Ferriferous oxide/carbon composition lithium ion battery cathode material, this material adopts above method described in any one technical scheme to prepare.
In order to realize the 3rd above-mentioned object, present invention employs following technical scheme:
Lithium ion battery negative, the negative material described in employing and binding agent, conductive agent are mixed to form slurry in a solvent, slurry are coated to Copper Foil, foam copper or nickel foam collection liquid surface, dry and after compacting, obtain lithium ion battery negative.
As preferably, the process making lithium ion battery negative is as follows: by described ferriferous oxide/carbon compound cathode materials, conductive agent and binding agent by 8:(0 ~ 2): the mass ratio of (0.5 ~ 2) joins in solvent and mixes, be coated on collector, then dry, obtained lithium ion battery negative.
In lithium ion battery negative of the present invention, described binding agent can use conventional binders well known by persons skilled in the art, as polyvinylidene difluoride (PVDF) (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber(SBR) (SBR) and Xylo-Mucine (CMC).
In lithium ion battery negative of the present invention, described collector can use conventional collector well known by persons skilled in the art, as Copper Foil, foam copper, nickel foam.
One or more in lithium ion battery negative of the present invention, in the acetylene black that conductive agent can adopt those skilled in the art to commonly use, carbon black, Ketjen black, graphite, carbon fiber.
In lithium ion battery negative of the present invention, the N-methyl-pyrrolidon (NMP) that solvent can adopt those skilled in the art to commonly use or water.
In order to realize the 4th above-mentioned object, present invention employs following technical scheme:
Lithium ion battery, the lithium ion battery that the negative pole described in this lithium ion battery adopts, the positive pole of removal lithium embedded and in-between barrier film and electrolytic solution form.
The positive electrode material of deintercalate lithium ions can adopt various conventional cathode active material well known by persons skilled in the art, as LiCoO
2, LiFePO
4, LiMnPO
4, LiMnO
2, LiMn
2o
4, LiVPO
4f, LiNiO
2.
In lithium ion battery of the present invention, ionogen can be common non-aqueous solution liquid well known by persons skilled in the art, and wherein in electrolytic solution, lithium salts can be lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), fluorocarbon based Sulfonic Lithium (LiC (SO
2cF
3)
3) in one or more.Non-aqueous solvent can be chain acid fat and ring-type acid fat mixing solutions, and wherein chain acid fat can be one or more in dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate fat (EMC); Ring-type acid fat can be one or more in ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate fat (VC).The concentration of electrolyte lithium salt is generally 0.7 ~ 1.3 mol/L.
After adopting technique scheme, beneficial effect of the present invention is as follows:
1. the advantage that the present invention gives prominence to the invention provides a kind of method preparing iron oxide/carbon composite material, and the method is simple, and production efficiency is high, is applicable to large-scale production, the cheap and wide material sources of the prices of raw and semifnished materials;
2. another advantage of the present invention is because carbon and ferriferous oxide are once formed simultaneously, and iron oxide particle to be mainly embedded in carbon or coated by carbon, and carbon is tight with contacting of ferriferous oxide.The introducing of carbon not only substantially increases the electronic conductivity of matrix material, also effectively suppress the volumetric expansion of ferriferous oxide in doff lithium process, reduce efflorescence, greatly can improve the utilising efficiency of matrix material, and ferriferous oxide maintains the characteristic of its heavy body in the composite.The amorphous compound also having advantage to be the ferriferous oxide obtained to be iron and oxygen of the present invention, Fe
3o
4, Fe
2o
3or hold concurrently containing above two-phase or three-phase;
3. iron oxide/carbon composite material provided by the invention is as lithium ion battery negative material, has the lithium storage content being several times as much as business carbon negative pole material.Iron oxide/carbon composite material provided by the invention as lithium ion battery negative material, its first loading capacity can reach 1380mAh/g, reversible capacity can reach 960mAh/g first, and the specific storage of material is high, and stable circulation is good;
4. the density of ferriferous oxide is about 5g/cm
3, be the density (2.2 ~ 2.4g/cm of carbon material
3) more than 2 times.Therefore, with ferriferous oxide/carbon compound cathode materials of the present invention, there is the tap density higher than current business carbon negative pole material, for lithium ion battery negative material, there is higher volume and capacity ratio.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of the iron oxide/carbon composite material that embodiment 1 obtains.
Fig. 2 is the scanning electron microscope pattern of the iron oxide/carbon composite material that embodiment 1 obtains.Insertion figure in figure is the selected diffraction figure of non-crystal oxide under transmission electron microscope existed in matrix material.
Fig. 3 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 1 obtains.
Fig. 4 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 2 obtains.
Fig. 5 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 3 obtains.
Fig. 6 is the x-ray diffraction pattern of the iron oxide/carbon composite material that embodiment 4 obtains.
Fig. 7 is the scanning electron microscope pattern of the iron oxide/carbon composite material that embodiment 4 obtains.
Fig. 8 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 4 obtains.
Fig. 9 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 5 obtains.
Figure 10 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 6 obtains.
Figure 11 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 7 obtains.
Figure 12 is the scanning electron microscope pattern of the iron oxide/carbon composite material that embodiment 8 obtains.
Figure 13 is the x-ray diffraction pattern of the iron oxide/carbon composite material that embodiment 8 obtains.
Figure 14 is the x-ray photoelectron spectroscopy of the iron oxide/carbon composite material that embodiment 8 obtains.
Figure 15 is the transmission electron microscope pattern of the iron oxide/carbon composite material that embodiment 8 obtains.Insertion figure in figure is the selected diffraction figure of non-crystal oxide under transmission electron microscope existed in matrix material.
Figure 16 is the cycle performance figure of ferriferous oxide/carbon compound cathode materials that embodiment 8 obtains.
Embodiment
The present invention may be better understood for following examples, but the present invention is not limited to following examples.In addition, after having read content of the present invention, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
embodiment 1
Adopt FeCl
3as source of iron, be made into the solution that volumetric molar concentration is 2.2 mol/L.This solution is heated to 100 DEG C, will with FeCl
3mol ratio is that the ammoniacal liquor (15 mol/L) of the ratio of 10:1 joins FeCl
3in the aqueous solution, and add and FeCl
3mol ratio is the citric acid of 3:1, goes into liquid form mixt after fully stirring.Above-mentioned solution is carried out spraying cracking in 400 DEG C of air, obtains powder presoma.Again by this powder presoma in a nitrogen atmosphere, within 3 hours, iron oxide/carbon composite material is obtained through 450 DEG C of calcinings.Detect through X-ray diffraction, in matrix material, crystalline oxide is mainly Fe
3o
4.Through elemental microanalysis method analysis, in matrix material, carbon content is 20% of composite weight per-cent.Diffraction analysis is chosen, also containing amorphous ferriferous oxide in matrix material through transmission electron microscope.
The preparation of negative pole: with N-methyl-pyrrolidon (NMP) for solvent, above-mentioned iron-based oxide/carbon matrix material is mixed by the quality proportioning of 8:1:1 with conductive agent acetylene black and binding agent polyvinylidene difluoride (PVDF) (PVDF), be coated in collector nickel foam, then 120 DEG C of oven dry, rolling formation after dry, cut-parts obtain the negative pole of desired size.
The preparation of lithium ion battery:
Be the iron lithium phosphate of 8:1:1 by weight ratio, conductive agent acetylene black, poly(vinylidene fluoride) (PVDF) join in N-methyl-pyrrolidon (NMP) solvent, obtained anode sizing agent after stirring; Anode sizing agent is coated on aluminium foil equably, after drying rolling formation, the lithium ion cell positive of obtained 53 millimeters of (length) × 30 millimeter (wide) of cut-parts.
Include in the square aluminum hull of 55 millimeters × 34 millimeters × 6 millimeters after obtained lithium ion cell positive, barrier film, negative pole successively lamination is good, by the lithium hexafluoro phosphate (LiPF containing 1 mol/L
6) ethylene carbonate: methylcarbonate (EC/DMC) by volume for 1:1:1 is made into electrolytic solution, inject electrolytic bath, sealed cell aluminum hull can obtain lithium ion battery.
Iron oxide/carbon composite material capacity and cycle performance test: adopt simulated battery to test the capacity of ferriferous oxide/carbon compound cathode materials prepared by the present embodiment and cycle performance.With N-methyl-pyrrolidon (NMP) for solvent, preparation-obtained iron oxide/carbon composite material, acetylene black and binding agent polyvinylidene difluoride (PVDF) (PVDF) are mixed by the quality proportioning of 8:1:1, be coated in collector nickel foam, then rear compacting is dried for 120 DEG C, obtained test electrode.With metallic lithium be test electrode to electrode, adopt 2025 type button cells to test.2025 button cell shells are put into, with the lithium hexafluoro phosphate (LiPF of 1 mol/L after good to test electrode, barrier film (Celgard2400), lithium tinsel successively lamination
6) ethylene carbonate: methylcarbonate (EC/DMC, volume ratio is 1:1) solution as electrolytic solution, at H
2o and O
2content is all less than in the glove box of 0.1ppm, adopts sealing machine sealed cell shell to obtain lithium ion battery.Neware battery test system (specification 5V, 2mA) is adopted to carry out constant current charge-discharge test to assembled simulated battery.Test current is 100mA/g, and voltage range is 0 ~ 3V.
Fig. 1 is the x-ray diffraction pattern of the iron oxide/carbon composite material that the present embodiment obtains.Visible, the crystalline oxide in matrix material is mainly Fe
3o
4, other is also containing a small amount of Fe
8+3(O, OH)
16cl
1.3by product.
Fig. 2 is the scanning electron microscope pattern of the iron oxide/carbon composite material that the present embodiment obtains, and matrix material forms primarily of the irregular particle of ferriferous oxide and carbon composition, and particle size is micron order.Insertion figure in figure is the selected diffraction figure in energy spectrum analysis iron content and oxygen region under transmission electron microscope in this matrix material, describes the existence of amorphous oxides.
Fig. 3 is the cyclic curve figure of the iron oxide/carbon composite material that the present embodiment obtains, and this material has heavy body and excellent cyclical stability concurrently as lithium ion battery negative material as seen.The electric discharge first of this ferriferous oxide/carbon material can reach 1370mAh/g, and reversible capacity is 960mAh/g first, and the capacity after 200 circulations is 850mAh/g, capability retention nearly 90%.Matrix material capacity only slightly declines in initial several working cycle, subsequently until 200 times circulation process in capacity almost do not decline.
embodiment 2
Adopt FeCl
3as source of iron, be made into the solution that volumetric molar concentration is 4.0 mol/L.At room temperature, add and FeCl in this solution
3mol ratio be the ammoniacal liquor (concentration is 8 mol/L) of 8:1, and then to add and FeCl
3mol ratio be the citric acid of 3:1, stir, formed liquid phase mixture.By above-mentioned liquid phase mixture in the air atmosphere of 400 DEG C, carry out spraying cracking, form powder body material.Again to this powder body material at N
2under atmosphere, within 3 hours, obtain iron oxide/carbon composite material through 500 DEG C of calcinings.Detect through X-ray diffraction, in matrix material, crystalline oxide is mainly Fe
3o
4.Through the selected diffraction analysis in transmission electron microscope energy spectrum analysis iron content and oxygen region, containing amorphous oxides in material.Through elemental microanalysis method analysis, in matrix material, carbon content is 15% of composite weight per-cent.
Adopt the method chemical property to this matrix material identical with embodiment 1 to test, the loading capacity first of material reaches 1380mAh/g, and reversible capacity reaches 960mAh/g first, and the capacity after 200 circulations is 780mAh/g, and capability retention is 76%.Fig. 4 is that the present embodiment obtains the cycle performance of matrix material as lithium ion battery negative material.
Adopt the method identical with embodiment 1 with this matrix material for negative material is prepared into negative pole and lithium ion battery.
embodiment 3
Adopt FeCl
3as source of iron, be made into the solution that volumetric molar concentration is 2.2 mol/L.This solution is heated to 50 DEG C, adds in the solution and FeCl
3mol ratio be that the ammoniacal liquor (1.5 mol/L) of 12:1 stirs, and then to add and FeCl
3mol ratio be the citric acid of 4:1, stir, formed liquid phase mixture.By above-mentioned liquid phase mixture in the air atmosphere of 300 DEG C, carry out spraying cracking, form powder body material.Again to this powder body material at N
2under atmosphere, within 3 hours, obtain iron oxide/carbon composite material through 450 DEG C of calcinings.Detect through X-ray diffraction, in matrix material, crystalline oxide is mainly Fe
3o
4.Through elemental microanalysis method analysis, in matrix material, carbon content is 25% of composite weight per-cent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this matrix material.The loading capacity first of this material is 1360mAh/g, and reversible capacity is 940mAh/g first, and the capacity after 200 circulations is 800mAh/g, and capability retention is 85%.Fig. 5 is the cycle performance curve of matrix material that the present embodiment obtains, visible material only in initial several circulations capacity slightly decline, subsequently until in 200 circulations capacity substantially remain unchanged.
The preparation of negative pole: with N-methyl-pyrrolidon (NMP) for solvent, by above-mentioned iron-based oxide/carbon matrix material: conductive agent Ketjen black: binding agent polyvinylidene difluoride (PVDF) (PVDF) mixes by the quality proportioning of 8:0.5:1, be coated in collector nickel foam, then 120 DEG C of oven dry, rolling formation after drying, cut-parts obtain the negative pole of desired size.
The preparation of lithium ion battery:
Be the LiCoO of 8:0.5:0.5:1 by weight ratio
2, conductive agent acetylene black, conductive agent carbon black, poly(vinylidene fluoride) (PVDF) join in N-methyl-pyrrolidon (NMP) solvent, obtained anode sizing agent after stirring; Anode sizing agent is coated on aluminium foil equably, after drying rolling formation, the lithium ion cell positive of obtained 53 millimeters of (length) × 30 millimeter (wide) of cut-parts.
Include in the square aluminum hull of 55 millimeters × 34 millimeters × 6 millimeters after obtained lithium ion cell positive, barrier film, negative pole successively lamination is good, ethylene carbonate by the lithium hexafluoro phosphate (LiPF6) containing 1 mol/L: methylcarbonate (EC/DMC) is by volume for 1:1:1 is made into electrolytic solution, inject electrolytic bath, sealed cell aluminum hull can obtain lithium ion battery.
embodiment 4
Adopt FeCl
3as source of iron, be mixed with the solution that volumetric molar concentration is 1.0 mol/L.According to FeCl
3the ratio being 5:1 with the mol ratio of ammonia adds ammoniacal liquor (15 mol/L) in solution, adds and FeCl
3mol ratio is that the citric acid of 2:1 stirs.Above-mentioned liquid phase mixture to be sprayed in the air of 450 DEG C cracking, form powder body material, then by above-mentioned materials at N
2in atmosphere, 450 DEG C of high-temperature calcinations obtain iron oxide/carbon composite material in 1 hour.Detect through XRD, the crystal mainly contained in matrix material is Fe mutually
3o
4.Through ultimate analysis, wherein the content of carbon is 19wt%.Fig. 6 is the X-ray diffracting spectrum of the matrix material that the present embodiment obtains.Fig. 7 is the scanning electron microscope pattern of this material, and the partial particulate of this material has porous pattern.
The method identical with embodiment 1 is adopted to test the chemical property of this material.Test result shows, the loading capacity first of this material is 1350mAh/g, and reversible capacity is 980mAh/g first.After 200 circulations, capacity maintains 810mAh/g.Fig. 8 is the cycle performance curve of the matrix material that the present embodiment obtains.
embodiment 5
With FeCl
3as source of iron, be mixed with saturated solution, will with FeCl
3mol ratio is ammoniacal liquor (concentration is 5 mol/L) and and the FeCl of 6:1
3mol ratio be that the citric acid of 2:1 mixes.Above-mentioned liquid phase mixture to be sprayed in 500 DEG C of air cracking, obtain iron oxide/carbon composite material.
The identical method of embodiment 1 is adopted to be assembled into simulated battery, the chemical property of test iron.
The loading capacity first of this material is 1190mAh/g, and reversible capacity is 870mAh/g first, the capacity of the 720mAh/g that still has an appointment after 200 circulations.Fig. 9 is the cycle performance curve of this material.
Adopt the method identical with embodiment 3 will be prepared to negative pole and lithium ion battery to material.
embodiment 6
Adopt ferric sulfate as source of iron, be made into saturated solution.This solution is heated to add in 60 DEG C of backward solution be the ammoniacal liquor (10 mol/L) of 1:1 with ferric sulfate mol ratio and be the lauric acid of 1:1 with the mol ratio of ferric sulfate, after being mixed evenly, to this liquid phase mixture under vacuum, at the temperature of-30 DEG C, lyophilize is carried out to it, obtain powder presoma.And then to this presoma at N
2under gas atmosphere, through 550 DEG C of calcinings 1 hour, obtain containing Fe
2o
3, Fe
3o
4with the matrix material of carbon.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.The loading capacity first of this material is 1130mAh/g, and reversible capacity is 790mAh/g first, and after 150 circulations, capacity is about 450mAh/g.Figure 10 is the cyclic curve figure of this material.
embodiment 7
Adopt FeCl
3as source of iron, be made into the solution that concentration is 2 mol/L.This solution is heated to add and FeCl in 60 DEG C of backward solution
3mol ratio is ammoniacal liquor (15 mol/L) and and the FeCl of 5:1
3mol ratio be the citric acid of 1:1, after being mixed evenly, to it, spraying cracking is carried out to this liquid phase mixture in air atmosphere at the temperature of 600 DEG C, obtains powder presoma.And then to this presoma at N
2under gas atmosphere, through 500 DEG C of calcinings 0.5 hour, obtain iron oxide/carbon composite material.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.The loading capacity first of this material is 1200mAh/g, and reversible capacity is 870mAh/g first, and after 150 circulations, capacity is about 620mAh/g.Figure 11 is the cyclic curve figure of this material.
embodiment 8
With FeCl
3for source of iron, by FeCl
3be mixed with saturated solution, will with FeCl
3mol ratio is respectively the ammoniacal liquor (concentration is 15 mol/L) of 3.5:1 and 1:1 and citric acid, and to add to above-mentioned be the FeCl of 80 DEG C to Heating temperature
3in solution, mix.This liquid phase mixture is carried out spraying dry.Drying temperature is 200 DEG C.The powder that drying is obtained under nitrogen protection 400 DEG C calcining 3 hours, obtain amorphous iron oxide/carbon composite material.Adopt elemental microanalysis method to analyze to the content of carbon in matrix material, in matrix material, the content of carbon is 29wt%.
Figure 12 is the scanning electron microscope pattern of this matrix material.
Figure 13 is the x-ray diffraction pattern of this matrix material, and this matrix material is amorphous phase as seen.
Figure 14 is the x-ray photoelectron spectroscopy figure of this matrix material, there is iron and oxygen element in matrix material, and wherein iron is mixed valence.
Figure 15 is the transmission electron microscope picture of this matrix material.Region relatively dark in figure is ferriferous oxide, and the region of light color is carbon relatively.Diffractogram in figure is the diffractogram of amorphous iron oxide compound.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.Figure 16 is the cyclic curve figure of this material.The loading capacity first of this material is 1310mAh/g, and reversible capacity is 850mAh/g first, and after 200 circulations, capacity is about 800mAh/g, does not almost fail.Matrix material has excellent cycle performance.
Adopt the method identical with embodiment 1 that this non-crystalline state iron oxide/carbon composite material is prepared into negative pole and lithium ion battery.
embodiment 9
Adopt iron protochloride as source of iron, be made into the solution that concentration is 1 mol/L.This solution is heated to add in 60 DEG C of backward solution be the ammoniacal liquor (10 mol/L) of 2:1 with iron protochloride mol ratio and be the glucose of 6:1 with the mol ratio of iron protochloride, after being mixed evenly, to it, spraying dry is carried out to this liquid phase mixture in air atmosphere at the temperature of 200 DEG C, obtains powder presoma.And then to this presoma under Ar gas atmosphere, through 500 DEG C of calcinings 3 hours, obtain iron oxide/carbon composite material, in matrix material, the content of carbon was 70% of matrix material mass percent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, test the chemical property of this material.The loading capacity first of matrix material is 1020mAh/g, and reversible capacity is 720mAh/g first, and after 50 circulations, capacity is 480mAh/g.
embodiment 10
Adopt FeCl
3as source of iron, be mixed with the solution that concentration is 1.5 mol/L.Add and FeCl in solution
3mol ratio is ammoniacal liquor (5 mol/L) and and the FeCl of 3:1
3mol ratio be the polyvinyl alcohol of 0.5:1, after being mixed evenly, to it, spraying dry is carried out to this liquid phase mixture in air atmosphere at the temperature of 150 DEG C, the product obtained is ground, obtain powder presoma.And then to this presoma at N
2under gas atmosphere, through 700 DEG C of calcinings 1 hour, obtain iron oxide/carbon composite material.The content of composite material carbon is 15% of matrix material mass percent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, the loading capacity first of testing the chemical property matrix material of this material is 990mAh/g, and reversible capacity is 710mAh/g first, and after 50 circulations, capacity is 510mAh/g.
embodiment 11
Adopt FeCl
3as source of iron, be mixed with the solution that concentration is 1.0 mol/L.Add and FeCl in solution
3mol ratio is ammoniacal liquor (5 mol/L) and and the FeCl of 3:1
3mol ratio be the lauric acid of 0.3:1, after being mixed evenly, to it, spraying dry is carried out to this liquid phase mixture in air atmosphere at the temperature of 150 DEG C, the product obtained is ground, obtain powder presoma.And then to this presoma in a hydrogen atmosphere, through 600 DEG C of calcinings 1 hour, obtain iron oxide/carbon composite material.The content of composite material carbon is 11% of matrix material mass percent.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, the loading capacity first of testing the chemical property matrix material of this material is 1010mAh/g, and reversible capacity is 780mAh/g first, and after 50 circulations, capacity is 668mAh/g.
embodiment 12
Employing iron protochloride as source of iron, is mixed with the solution that concentration is 2.0 mol/L as source of iron.Add and FeCl in solution
3mol ratio is ammoniacal liquor (5 mol/L) and and the FeCl of 3:1
3mol ratio be the citric acid of 0.5:1, after being mixed evenly, to it, spraying dry is carried out to this liquid phase mixture in air atmosphere at the temperature of 200 DEG C, the product obtained is ground, obtain powder presoma.And then to this presoma under the mixed atmosphere of nitrogen and 10% hydrogen (volume ratio), through 550 DEG C of calcinings 2 hours, obtain iron oxide/carbon composite material.
Adopt the identical method of embodiment 1 to be assembled into simulated battery, the loading capacity first of testing the chemical property matrix material of this material is 970mAh/g, and reversible capacity is 752mAh/g first, and after 50 circulations, capacity is 516mAh/g.
Claims (18)
1. a preparation method for iron oxide/carbon composite material, is characterized in that the method comprises the following steps:
1) with water-soluble molysite for source of iron, with Water Soluble Organic Carbon source for carbon source, molysite aqueous solution and ammoniacal liquor and organic carbon source are mixed, obtain liquid phase mixture; The mol ratio of water-soluble molysite and ammoniacal liquor is 1:(0.2 ~ 20); The mol ratio in water-soluble molysite and Water Soluble Organic Carbon source is 1:(0.2 ~ 8); The Water Soluble Organic Carbon source adopted is one or more in citric acid, lauric acid, sucrose, glucose and polyvinyl alcohol;
2) adopt the method for spraying dry, lyophilize or cracking of spraying to form powder presoma to this liquid phase mixture, then this powder presoma is calcined, be prepared into iron oxide/carbon composite material; Or directly spraying cracking is carried out to this liquid phase mixture, be prepared into iron oxide/carbon composite material; In described iron oxide/carbon composite material, the content of carbon is 5 ~ 70wt% of matrix material mass percent, and described ferriferous oxide comprises amorphous compound, FeO, Fe of iron and oxygen
3o
4, Fe
2o
3in one or more.
2. the preparation method of iron oxide/carbon composite material according to claim 1, is characterized in that: the content of carbon is 20 ~ 60% of matrix material mass percent.
3. the preparation method of iron oxide/carbon composite material according to claim 1 and 2, is characterized in that: water-soluble molysite is one or more mixing in iron trichloride, iron protochloride, ironic oxalate, iron nitrate, ferric sulfate and ferrous sulfate and their crystalline hydrate.
4. the preparation method of iron oxide/carbon composite material according to claim 1 and 2, is characterized in that: water-soluble molysite is iron trichloride or its crystalline hydrate.
5. the preparation method of iron oxide/carbon composite material according to claim 1 and 2, it is characterized in that the volumetric molar concentration of water-soluble molysite is the saturated volumetric molar concentration of 0.5 mol/L ~ water-soluble molysite, the concentration of ammoniacal liquor is 3 ~ 15 mol/L.
6. the preparation method of iron oxide/carbon composite material according to claim 5, is characterized in that the mol ratio of water-soluble molysite and ammoniacal liquor is 1:(1 ~ 5); The mol ratio in water-soluble molysite and Water Soluble Organic Carbon source is 1:(0.5 ~ 5).
7. the preparation method of iron oxide/carbon composite material according to claim 1 and 2, is characterized in that: liquid phase mixture adopts spraying dry to prepare powder presoma, and drying temperature is 100 ~ 500 DEG C; Dry atmosphere can adopt the mixed gas of air, nitrogen, argon gas or more one or more gases; Then, calcine the powder presoma that drying obtains, calcining temperature is 300 ~ 900 DEG C; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or more one or more gases; The time of calcining is 0.5 ~ 6 hour.
8. the preparation method of iron oxide/carbon composite material according to claim 1 and 2, is characterized in that: liquid phase mixture adopts spraying dry to prepare powder presoma, and drying temperature is 150 ~ 400 DEG C; Dry atmosphere is air; Then, calcine the powder presoma that drying obtains, calcining temperature is 350 ~ 700 DEG C; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or more one or more gases; The time of calcining is 1 ~ 4 hour.
9. the preparation method of iron oxide/carbon composite material according to claim 1 and 2, it is characterized in that: liquid phase mixture is under the mixed gas of one or more gases of air, nitrogen, argon gas or more, to spray at 300 ~ 900 DEG C cracking, directly form iron oxide/carbon composite material.
10. the preparation method of iron oxide/carbon composite material according to claim 9, is characterized in that: spraying cracking temperature is 350 ~ 800 DEG C, and cracking atmosphere adopts air.
The preparation method of 11. iron oxide/carbon composite material according to claim 1 and 2, it is characterized in that: liquid phase mixture is sprayed at the mixed gas of one or more gases of air, nitrogen, argon gas or more and is cracked into powder presoma at 100 ~ 500 DEG C, and then at 300 ~ 900 DEG C, calcine 0.5 ~ 6 hour in an inert atmosphere, form iron oxide/carbon composite material; Inert atmosphere is the mixed gas of nitrogen, argon gas or nitrogen and argon gas.
The preparation method of 12. iron oxide/carbon composite material according to claim 11, is characterized in that: cracking atmosphere adopts air.
The preparation method of 13. iron oxide/carbon composite material according to claim 11, is characterized in that: calcination atmosphere adopts nitrogen, and calcination time is 1 ~ 4 hour.
The preparation method of 14. iron oxide/carbon composite material according to claim 1 and 2, is characterized in that: liquid phase mixture adopts lyophilize to prepare powder presoma, and drying temperature is-10 ~-70 DEG C, and adopts dynamic vacuum; Then, calcine the powder presoma that drying obtains, calcining temperature is 300 ~ 900 DEG C; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or more one or more gases; The time of calcining is 0.5 ~ 6 hour.
The preparation method of 15. iron oxide/carbon composite material according to claim 1 and 2, is characterized in that: liquid phase mixture adopts lyophilize to prepare powder presoma, and drying temperature is-20 ~-50 DEG C, and adopts dynamic vacuum; Then, calcine the powder presoma that drying obtains, calcining temperature is 350 ~ 700 DEG C; Calcination atmosphere can adopt the mixed gas of air, nitrogen, argon gas, hydrogen, methane, ammonia or more one or more gases; The time of calcining is 1 ~ 4 hour.
Ferriferous oxide/carbon composition lithium ion battery cathode material that 16. methods according to claim 1 ~ 15 any one claim prepare.
17. lithium ion battery negatives, it is characterized in that: adopt negative material according to claim 16 and binding agent, conductive agent to be mixed to form slurry in a solvent, slurry is coated to Copper Foil, foam copper or nickel foam collection liquid surface, dries and after compacting, obtain lithium ion battery negative.
18. lithium ion batteries, is characterized in that: this lithium ion battery adopts the lithium ion battery of the positive pole of negative pole according to claim 17, removal lithium embedded and in-between barrier film and electrolytic solution composition.
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| CN104045116B (en) * | 2014-06-12 | 2016-01-27 | 江苏大学 | The preparation method of nano porous metal oxide/carbon lithium ion battery negative material |
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