CN104009225A - Method for synthesis of lithium iron silicate/crystallized carbon composite positive electrode material - Google Patents
Method for synthesis of lithium iron silicate/crystallized carbon composite positive electrode material Download PDFInfo
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- CN104009225A CN104009225A CN201410199194.2A CN201410199194A CN104009225A CN 104009225 A CN104009225 A CN 104009225A CN 201410199194 A CN201410199194 A CN 201410199194A CN 104009225 A CN104009225 A CN 104009225A
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- lithium
- temperature
- carbon composite
- composite positive
- rice husk
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title abstract 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 title abstract 3
- 230000015572 biosynthetic process Effects 0.000 title abstract 2
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 75
- 241000209094 Oryza Species 0.000 claims abstract description 68
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 68
- 239000010903 husk Substances 0.000 claims abstract description 68
- 235000009566 rice Nutrition 0.000 claims abstract description 68
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 41
- 238000000197 pyrolysis Methods 0.000 claims abstract description 40
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000005554 pickling Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001238 wet grinding Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- ZNDKHNUDMXNQMF-UHFFFAOYSA-N [Li].[Fe].[Si](O)(O)(O)O Chemical compound [Li].[Fe].[Si](O)(O)(O)O ZNDKHNUDMXNQMF-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 238000010000 carbonizing Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000009938 salting Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 150000003891 oxalate salts Chemical class 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229920005610 lignin Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 230000004907 flux Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229940062993 ferrous oxalate Drugs 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910009731 Li2FeSiO4 Inorganic materials 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013318 LiMSiO4 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for synthesis of a lithium iron silicate/crystallized carbon composite positive electrode material, and belongs to the technical field of lithium ion battery. The method comprises the steps: pickling rice husks, washing, filtering and drying to obtain rice husks having alkali metal oxide impurities removed; under an oxygen-free or aerobic condition, carrying out low-temperature pyrolysis of the rice husks having the alkali metal oxide impurities removed to obtain pyrolyzed rice husks; adding the obtained pyrolyzed rice husks into a transition metal M1 precursor salt solution, and then carrying out a catalytic carbonization reaction at a high temperature to obtain a catalytic carbonized product; carrying out low temperature oxidation of the catalytic carbonized product to obtain an oxidative product; adding an iron source and a lithium source into the oxidative product, carrying out wet grinding to obtain a mixed material, and then drying the mixed material; and under an inert atmosphere, baking the dried mixed material at the temperature of 500-800 DEG C for 1-20 h, and thus obtaining the lithium iron silicate/crystallized carbon composite positive electrode material. The method improves the crystallinity of carbon in the silicate/carbon composite positive electrode material prepared from the rice husks.
Description
Technical field
A kind of method that the present invention relates to synthetic silicic acid iron lithium/crystalline carbon composite positive pole, belongs to technical field of lithium ion.
Background technology
Fast development along with electronics and information industry, mobile communication, digital vedio recording and portable computer are used widely, the development of electric automobile and exploitation be also carrying out extensively and profoundly, thereby drive the developing rapidly of device-lithium ion battery that the energy is provided for the said equipment.Compare with nickel-cadmium cell with traditional Ni-MH battery, it is high that lithium ion battery has energy density, operating voltage is high, self discharge is little, can fast charging and discharging, the advantage such as security performance is good, be with fastest developing speed, a kind of secondary cell that market prospects are the brightest at present.
The performance that in lithium ion battery, battery material is determined to battery plays decisive influence effect.1996, Goodenough seminar proposed olivine-type LiFePO4 positive electrode first, and Armand proposes another kind of take the orthosilicate positive electrode that SiO4 tetrahedron is polyanion group, i.e. LiMSiO4(M=Fe, Mn etc. at patent US6085015).This type of positive electrode has stable SiO
4tetrahedron skeleton, abundant natural resources, advantages of environment protection, in addition, it can allow 2 reversible de-embeddings of Li+ in theory, and theoretical capacity reaches 330mAh/g.But it is after discharging and recharging for the first time, and great changes will take place for structure, thereby affect the reversible de-embedding of lithium ion, hindered its application.In fact, the silicate anodal material that the ferric metasilicate lithium of take is representative can only take off 1 lithium ion of embedding in the use, causes its theoretical capacity only to have 166mAh/g.At present, people by surface be coated, the method such as metal-doped and synthesizing nano-particle improves its chemical property, wherein carbon is coated is comparatively common method of modifying.
Rice husk contains amorphous nano silicon and macromolecule organic matter (cellulose, hemicellulose and lignin etc.), is synthetic silicate and then the coated desirable feedstock of original position carbon.
In carbon is coated, the crystallinity of carbon-coating has very important impact to its electric conductivity.Liu Qinglei etc. be take rice husk as raw material, adopt transition metal as catalyst, the amorphous carbon based composites with crosslinked carbon nanobelts network is prepared in high-temperature catalytic charing, and studied its capability of electromagnetic shielding [Liu QL, Zhang D, Fan TX, Gu JJ, Miyamoto Y, Chen ZX. Amorphous carbon-matrix composites with interconnected carbon nano-ribbon networks for electromagnetic interference shielding. Carbon, 2008,46:461 – 465.].Result shows, the good carbon nanobelts of crystallinity can significantly improve the electric conductivity of material.Purification research to CNT (carbon nano-tube) shows, the structural stability of amorphous carbon is weaker than the feature of crystallinity charcoal, by 500 ℃ of air oxidations, can be significantly except the amorphous carbon in mixed structure material with carbon element, obtain better material with carbon element [the Bera D of (conductivity is higher) of crystallinity, Perrault JP, Heinrich H, Seal S. Defect studies on as-synthesized and purified carbon nanostructures produced by arc-discharge in solution process. Journal of nanoscience and nanotechnology, 2006, 6:1084-1091.].
Chinese patent application CN103346300A proposes to take the method that rice husk is raw material synthetic silicate/carbon composite anode material, and in the method, the structure of carbon is amorphous carbon, and conductivity is poor; In addition, the more difficult control of the content of carbon in composite positive pole, thus affected the pay(useful) load amount of active material in composite positive pole.
Summary of the invention
For problem and the deficiency of above-mentioned prior art existence, the invention provides a kind of method of synthetic silicic acid iron lithium/crystalline carbon composite positive pole.This method is improved the crystallinity of carbon in silicate/carbon composite anode material prepared by above-mentioned rice husk, and the pay(useful) load that improves active material in composite material, thereby improves the chemical property of material, and the present invention is achieved through the following technical solutions.
A method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first by rice husk pickling, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under anaerobic or aerobic conditions;
(3) pyrolysis rice husk step (2) being obtained is that 20～80:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature, be to carry out high-temperature catalytic carbonization reaction 1h～5h under 700 ℃～1000 ℃ conditions, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is that transition metal M 1 salt, flux are the solution that water, ethanol or acetone form;
(4) catalyzing and carbonizing product step (3) being obtained is that under 300 ℃～600 ℃ conditions, low-temperature oxidation 0.1h～4h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and iron, lithium mol ratio, be that 1:1:2 adds source of iron and lithium source and adds water or ethanol wet-milling 3～20h obtains mixed material, then that mixed material is dry;
(6), under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 500～800 ℃ of roasting 1～20h can prepare silicate/crystalline carbon composite positive pole.
Described rice husk comprises following mass percent component: crude fibre 35.5%～45%, lignin 21%～26%, ash content 11.4%～22%, and silica 1 0%～21%, ash content is mainly silicon dioxide, all the other are alkali metal oxide.
The acid of the acid cleaning process in described step (1) is HCl, HNO
3or H
2sO
4, its concentration is 5wt%～40wt%, pickling time is 1h～10h, washs as deionized water washing is until pH is 6～7.
The condition of the low temperature pyrogenation in described step (2) is: the temperature of pyrolysis is 300 ℃～600 ℃, and pyrolysis time is 0.1h～4h.
One or several arbitrary proportion mixtures in the nitrate that middle transition metal M 1 salt of described step (3) is iron, cobalt, nickel, acetate, oxalates, chlorate, sulfate, the addition of transition metal M 1 salt is that 0.5～6:100 adds according to transition metal M 1 with the mass ratio of the pyrolysis rice husk of step (2) gained.
One or several arbitrary proportion mixtures in the oxide that in described step (5), source of iron is iron, carbonate, acetate, oxalates.
Lithium source in described step (5) is one or several arbitrary proportion mixtures in lithium carbonate, lithium acetate, lithia, lithium hydroxide, lithium sulfate, lithium nitrate, lithium phosphate.
The described inert atmosphere of above-mentioned steps (6) is the atmosphere under nitrogen, argon gas, helium or their mist.
The invention has the beneficial effects as follows: it is silicon source and carbon source that (1) this method is utilized cheap agricultural wastes rice husk simultaneously, prepares silicate/crystallinity carbon composite anode material, has realized the value added applications of agricultural wastes; (2) this method, by the catalysis carbonization of rice husk, forms crystallinity carbon, by the low-temperature oxidation of catalysis carbonization rice husk, remove the poor amorphous carbon of conductivity, control carbon content simultaneously, prepare silicate/crystallinity carbon composite anode material, improve conductivity and the active material load capacity of material.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first by the pickling of 500g rice husk, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity, wherein rice husk comprises following mass percent component: crude fibre 45%, lignin 26%, ash content 11.4%, silica 1 0%; The acid of acid cleaning process is HCl, and its concentration is 5wt%, and pickling time is 10h, washs as deionized water washing is until pH is 6～7;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under oxygen free condition, and wherein the temperature of pyrolysis is 600 ℃, and pyrolysis time is 0.1h;
(3) pyrolysis rice husk step (2) being obtained is that 80:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature, be under 700 ℃ of conditions, to carry out high-temperature catalytic carbonization reaction 5h, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is that transition metal M 1 salt, flux are the solution that water forms; Transition metal is nitrate and the acetate of quality 1:1 iron, and the addition of transition metal M 1 salt is that 6:100 adds according to transition metal M 1 with the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) being obtained is that under 600 ℃ of conditions, low-temperature oxidation 0.1h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and iron, lithium mol ratio, be that 1:1:2 adds transition metal source of iron and lithium source and adds ethanol wet-milling 10h to obtain mixed material, then mixed material is dry, the oxalates (ferrous oxalate) that wherein source of iron is iron, lithium source is lithium carbonate;
(6) under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 700 ℃ of roasting 15h can prepare silicate/crystalline carbon composite positive pole, inert atmosphere is for to pass under 300ml/min condition of nitrogen gas.
Above-mentioned Li2FeSiO4/ crystallinity carbon composite is prepared into battery.Concrete steps are as follows: Li2FeSiO4/ crystallinity carbon composite: conductive agent acetylene black: binding agent PVDF=8:1:1 (mass ratio) mixes, and are uniformly coated on the aluminium foil that thickness is 20 μ m, and 80 ℃ of vacuumize 10h, make positive plate.Take lithium metal as negative pole, 1MLiPF6 solution (solvent is the EC/EMC of volume ratio 1:1) be electrolyte, barrier film is Celgard2400, is assembled into button cell (CR2025) in argon gas atmosphere glove box.More than LAND battery charging and discharging test, carry out charge-discharge test, work system is: constant current charges and discharge, charging and discharging currents 1/16C, charging/discharging voltage are 1.5V～4.8V (vs.Li+/Li).First charge-discharge capacity 140mA/g, is 135mA/g after 20 circulations, and capability retention is 96.4%.
Embodiment 2
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first by rice husk pickling, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity, wherein rice husk comprises following mass percent component: crude fibre 35.5%, lignin 21%, ash 22%, silicon dioxide 21%; The acid of acid cleaning process is HCl, and its concentration is 40wt%, and pickling time is 2h, washs as deionized water washing is until pH is 6～7;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under oxygen free condition, and wherein the temperature of pyrolysis is 400 ℃, and pyrolysis time is 0.5h;
(3) pyrolysis rice husk step (2) being obtained is that 20:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature, be under 1000 ℃ of conditions, to carry out high-temperature catalytic carbonization reaction 2h, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is that transition metal M 1 salt, flux are the solution that ethanol forms, transition metal M 1 salt is that mass ratio is nitrate and the acetate of 1:1 iron, and the addition of transition metal M 1 salt is that 0.5:100 adds according to transition metal M 1 with the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) being obtained is that under 450 ℃ of conditions, low-temperature oxidation 0.5h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and iron, lithium mol ratio, be that 1:1:2 adds source of iron and lithium source and adds water wet-milling 10h to obtain mixed material, then mixed material is dry, the oxalates (ferrous oxalate) that wherein source of iron is iron, lithium source is lithium acetate;
(6) under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 650 ℃ of roasting 20h can prepare silicate/crystalline carbon composite positive pole, wherein inert atmosphere is to pass into the condition of nitrogen gas that flow is 300ml/min.
The chemical property of the method test material identical with embodiment 1.First charge-discharge capacity 138mA/g, is 136.6mA/g after 20 circulations, and capability retention is 99%.
Embodiment 3
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first by rice husk pickling, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity, wherein rice husk comprises following mass percent component: crude fibre 40.3%, lignin 23.5%, ash content 16.7%, silica 1 5.5%; The acid of acid cleaning process is H
2sO
4, its concentration is 20wt%, pickling time is 9h, washs as deionized water washing is until pH is 6～7;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions; Wherein pyrolysis temperature is 500 ℃, and pyrolysis time is 1h;
(3) pyrolysis rice husk step (2) being obtained is that 50:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature is under 900 ℃ of conditions, to carry out high-temperature catalytic carbonization reaction 4h, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is transition metal M 1 salt, flux is the solution that acetone forms, transition metal salt is the oxalates of the nickel of quality 1:1:1, hydrochloride, sulfate, the addition of transition metal M 1 salt is that 3.3:100 adds according to transition metal M 1 with the mass ratio of the pyrolysis rice husk of step (2) gained,
(4) catalyzing and carbonizing product step (3) being obtained is that under 400 ℃ of conditions, low-temperature oxidation 3h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and iron, lithium mol ratio, be that 1:1:2 adds source of iron and lithium source and adds ethanol wet-milling 10h to obtain mixed material, then mixed material is dry, the oxalates (ferrous oxalate) that wherein source of iron is iron, lithium source is lithium hydroxide;
(6) under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 800 ℃ of roasting 10h can prepare silicate/crystalline carbon composite positive pole, wherein inert atmosphere is to pass into the helium condition that flow is 300ml/min.
According to method identical in embodiment 1, carry out the Integration Assembly And Checkout of battery, test result: first charge-discharge capacity 150 mA/g are 148mA/g after 20 circulations, and capability retention is 98.7%.
Embodiment 4
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first by rice husk pickling, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity, wherein rice husk comprises following mass percent component: crude fibre 40.3%, lignin 23.5%, ash content 16.7%, silica 1 5.5%, the acid of acid cleaning process is HNO
3, its concentration is 20wt%, pickling time is 1h, washs as deionized water washing is until pH is 6～7;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions, and wherein pyrolysis temperature is 300 ℃, and pyrolysis time is 4h;
(3) pyrolysis rice husk step (2) being obtained is that 50:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature, be under 950 ℃ of conditions, to carry out high-temperature catalytic carbonization reaction 4h, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is that transition metal M 1 salt, flux are the solution that water forms, transition metal salt is oxalates, chlorate, the nitrate of the cobalt of quality 1:1:1, and the addition of transition metal M 1 salt is that 4:100 adds according to transition metal M 1 with the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) being obtained is that under 400 ℃ of conditions, low-temperature oxidation 1.5h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and metal M 1, lithium mol ratio, be that 1:1:2 adds source of iron and lithium source and adds ethanol wet-milling 12h to obtain mixed material, then mixed material is dry, the acetate (ferrous acetate) that wherein transition metal source of iron is iron, lithium source is lithium nitrate;
(6) under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 720 ℃ of roasting 13h can prepare silicate/crystalline carbon composite positive pole, wherein inert atmosphere is to pass into the argon gas condition that flow is 300ml/min.
According to method identical in embodiment 1, carry out the Integration Assembly And Checkout of battery, test result: first charge-discharge capacity 145mA/g is 143mA/g after 20 circulations, and capability retention is 98.6%.
Embodiment 5
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first by rice husk pickling, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity, wherein rice husk comprises following mass percent component: crude fibre 45%, lignin 26%, ash content 11.4%, silica 1 0%; The acid of acid cleaning process is HCl, and its concentration is 5wt%, and pickling time is 10h, washs as deionized water washing is until pH is 6～7;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions, and wherein the temperature of pyrolysis is 450 ℃, and pyrolysis time is 2h;
(3) pyrolysis rice husk step (2) being obtained is that 50:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature, be under 800 ℃ of conditions, to carry out high-temperature catalytic carbonization reaction 1h, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is that transition metal M 1 salt, flux are the solution that ethanol forms, the nitrate that transition metal M 1 salt is iron, the addition of transition metal M 1 salt is that 5.5:100 adds according to transition metal M 1 with the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) being obtained is that under 450 ℃ of conditions, low-temperature oxidation 2.5h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and iron, lithium mol ratio, be that 1:1:2 adds source of iron and lithium source and adds water wet-milling 3h to obtain mixed material, then mixed material is dry, wherein source of iron is the oxide (ferrous oxide) of quality 1:1 iron, the mixture of carbonate (ferric carbonate), and lithium source is the lithia of quality 1:1 and the mixture of lithium sulfate;
(6) under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 500 ℃ of roasting 1h can prepare silicate/crystalline carbon composite positive pole, wherein inert atmosphere is be 1:1 at mass ratio nitrogen and the mist condition of argon gas.
According to method identical in embodiment 1, carry out the Integration Assembly And Checkout of battery, test result: first charge-discharge capacity 147mA/g is 144mA/g after 20 circulations, and capability retention is 98.0%.
Embodiment 6
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first by rice husk pickling, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity, wherein rice husk comprises following mass percent component: crude fibre 35.5%, lignin 21%, ash 22%, silicon dioxide 21%; The acid of acid cleaning process is HCl, and its concentration is 40wt%, and pickling time is 2h, washs as deionized water washing is until pH is 6～7;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions, and wherein the temperature of pyrolysis is 400 ℃, and pyrolysis time is 3h;
(3) pyrolysis rice husk step (2) being obtained is that 50:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature, be under 900 ℃ of conditions, to carry out high-temperature catalytic carbonization reaction 1h, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is that transition metal M 1 salt, flux are the solution that acetone forms;
(4) catalyzing and carbonizing product step (3) being obtained is that under 300 ℃ of conditions, low-temperature oxidation 2h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and iron, lithium mol ratio, be that 1:1:2 adds source of iron and lithium source and adds ethanol wet-milling 20h to obtain mixed material, then mixed material is dry, the oxalates (ferrous oxalate) that wherein source of iron is iron, lithium source is lithium carbonate;
(6) under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 700 ℃ of roasting 20h can prepare silicate/crystalline carbon composite positive pole, wherein inert atmosphere is under nitrogen atmosphere condition.
According to method identical in embodiment 1, carry out the Integration Assembly And Checkout of battery, test result: first charge-discharge capacity 150mA/g is 145mA/g after 20 circulations, and capability retention is 96.7%.
Claims (7)
1. a method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole, is characterized in that concrete steps are as follows:
(1) first by rice husk pickling, washing, filtration and dry after obtain removing the rice husk of alkali metal oxide impurity;
(2) rice husk of removal alkali metal oxide impurity step (1) being obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under anaerobic or aerobic conditions;
(3) pyrolysis rice husk step (2) being obtained is that 20～80:1ml/g joins in the presoma salting liquid of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature, be to carry out high-temperature catalytic carbonization reaction 1h～5h under 700 ℃～1000 ℃ conditions, obtain catalyzing and carbonizing product, wherein presoma salting liquid is that solute is that transition metal M 1 salt, flux are the solution that water, ethanol or acetone form;
(4) catalyzing and carbonizing product step (3) being obtained is that under 300 ℃～600 ℃ conditions, low-temperature oxidation 0.1h～4h obtains oxidation product in aerobic, low-temperature oxidation temperature;
(5) in the oxidation product obtaining to step (4), according to the silicon dioxide in oxidation product and iron, lithium mol ratio, be that 1:1:2 adds source of iron and lithium source and adds water or ethanol wet-milling 3～20h obtains mixed material, then that mixed material is dry;
(6), under inert atmosphere, by the dried mixed material of step (5), in temperature, be that 500～800 ℃ of roasting 1～20h can prepare silicate/crystalline carbon composite positive pole.
2. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, it is characterized in that: described rice husk comprises following mass percent component: crude fibre 35.5%～45%, lignin 21%～26%, ash content 11.4%～22%, silica 1 0%～21%, ash content is mainly silicon dioxide, and all the other are alkali metal oxide.
3. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: the acid of the acid cleaning process in described step (1) is HCl, HNO
3or H
2sO
4, its concentration is 5wt%～40wt%, pickling time is 1h～10h, washs as deionized water washing is until pH is 6～7.
4. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: the condition of the low temperature pyrogenation in described step (2) is: the temperature of pyrolysis is 300 ℃～600 ℃, and pyrolysis time is 0.1h～4h.
5. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, it is characterized in that: one or several arbitrary proportion mixtures in the nitrate that middle transition metal M 1 salt of described step (3) is iron, cobalt, nickel, acetate, oxalates, chlorate, sulfate, the addition of transition metal M 1 salt is that 0.5～6:100 adds according to transition metal M 1 with the mass ratio of the pyrolysis rice husk of step (2) gained.
6. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: one or several arbitrary proportion mixtures in the oxide that in described step (5), source of iron is iron, carbonate, acetate, oxalates.
7. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: the lithium source in described step (5) is one or several arbitrary proportion mixtures in lithium carbonate, lithium acetate, lithia, lithium hydroxide, lithium sulfate, lithium nitrate, lithium phosphate.
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