CN1369435A - Process for preparing spherical V2O3 and lithium vanadate as anode material of Li-ion battery - Google Patents
Process for preparing spherical V2O3 and lithium vanadate as anode material of Li-ion battery Download PDFInfo
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- CN1369435A CN1369435A CN02116311A CN02116311A CN1369435A CN 1369435 A CN1369435 A CN 1369435A CN 02116311 A CN02116311 A CN 02116311A CN 02116311 A CN02116311 A CN 02116311A CN 1369435 A CN1369435 A CN 1369435A
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- colloidal sol
- spherical
- lithium
- vanadate
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 239000010405 anode material Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 43
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 229910007086 Li1+xV3O8 Inorganic materials 0.000 abstract 1
- 229910003206 NH4VO3 Inorganic materials 0.000 abstract 1
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 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
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for preparing spherical V2O5 and lithium vanadate used as positive electrode material of Li-ion battery includes smelting NH4VO3, quick cooling in deionized water to generate V2O5 sol, spray drying to obtain spherical V2O5, adding LiOH to V2O5 sol, doping with CO, Ni, or Al, spray drying and heat treating to obtain spherical doped Li1+xV3O8. Its advantages are high stack density, high specific capacity and improved electrochemical performance.
Description
Technical field
The present invention relates to a kind of lithium ion battery anode material spherical vanadic anhydride (V for preparing
2O
5) and lithium vanadate (Li
1+xV
3O
8) process, belong to Chemical Engineering and new material technology field.
Background technology
The at present research to lithium ion anode material mainly concentrates on LiCoO
2, LiNiO
2, LiMnO
2And LiMn
2O
4On the different materials, and less to the research of vanadium based material, but the advantage such as vanadium is positive electrode has that cost is low, good cycle and high recycle ratio capacity.V wherein
2O
5And Li
1+xV
3O
8It all is good anode material for lithium-ion batteries.The V that sell present market
2O
5Powder and with NH
4VO
3The V that adopts high temperature solid state reaction to make for raw material
2O
5Powder is not spherical in shape, and bulk density is low, and capacity is very low during as anode material for lithium-ion batteries, and cycle performance is poor.Li
1+xV
3O
8The traditional preparation process method be to adopt high temperature solid state reaction, with Li
2CO
3And NH
4VO
3React the long period than at high temperature and obtain by certain metering.This method was both time-consuming, and energy consumption is high again, and the performance of product is also very poor.In recent years, people have adopted sol-gel process to synthesize Li
1+xV
3O
8, replace the method for above-mentioned high temperature solid state reaction, greatly improved the performance of product.But in existing method, be to prepare V by ion exchange resin earlier
2O
5Colloidal sol adds LiOH, heat-treats preparation Li after directly adding the thermosetting gel
1+xV
3O
8
Summary of the invention
The objective of the invention is to propose a kind of spherical V 2 (V for preparing
2O
5) and spherical lithium vanadate (Li
1+xV
3O
8) new technology and the new technology of dry colloidal sol, simplifying the preparation technology of positive electrode active materials, and the doping by other element (for example Co, Ni, Al), further improve the chemical property of material.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of lithium ion battery anode material spherical Vanadium Pentoxide in FLAKES, this method comprise following each step successively:
(1) take by weighing a certain amount of ammonium meta-vanadate, in retort furnace, it be warming up to 750 ℃～1000 ℃ fusions, be incubated after 1～3 hour, in the deionized water with its chilling vigorous stirring under room temperature, get final product Vanadium Pentoxide in FLAKES colloidal sol;
(2) the resulting gluey slurry of step (1) is carried out spraying drying, use the peristaltic pump charging, speed is 10-20mL/min, under 0.1Mpa, produce atomizing, the control air inlet temperature is 300 ± 5 ℃, and temperature out is 100 ± 5 ℃, promptly makes spherical V 2 colloidal sol powder after drying.
A kind of preparation method of lithium ion battery anode material spherical lithium vanadate, this method comprise following each step successively:
(1) take by weighing a certain amount of ammonium meta-vanadate, in retort furnace, it be warming up to 750 ℃～1000 ℃ fusions, be incubated after 1～3 hour, in the deionized water with its chilling vigorous stirring under room temperature, get final product Vanadium Pentoxide in FLAKES colloidal sol.
(2) add lithium hydroxide solution in the Vanadium Pentoxide in FLAKES colloidal sol of step (1) gained, the amount of the lithium hydroxide that is added continues to stir 3～6 hours in the preparation of 2: 3 ratio of lithium vanadium mol ratio, obtains finely dispersed colloidal sol;
(3) the resulting gluey slurry of step (2) is carried out spraying drying, use the peristaltic pump charging, speed is 10-20mL/min, produces atomizing under 0.1Mpa, and the control air inlet temperature is 300 ± 5 ℃, and temperature out is 100 ± 5 ℃, makes spherical powder;
(4) with the thermal treatment 3～6 hours under 300 ℃～400 ℃ conditions of the spherical powder of step (3) gained, promptly obtain spherical lithium vanadate product.
A kind of described lithium vanadate is carried out adulterated method, this method comprises following each step successively:
(1) mol ratio by Xiao Suangu and sodium hydroxide is 1: 2, the mol ratio of nickelous nitrate and sodium hydroxide is 1: 2, aluminum nitrate and the mol ratio of sodium hydroxide are that 1: 3 metering mixes under agitation condition with sodium hydroxide solution respectively than with Xiao Suangu, nickelous nitrate and aluminum nitrate solution, under 20 ℃～40 ℃ temperature condition, stirred 2～4 hours, after repeated centrifugation, the washing, make cobaltous hydroxide, nickel hydroxide, alumine hydroxide colloid respectively again;
(2) add lithium hydroxide solution in Vanadium Pentoxide in FLAKES colloidal sol, the amount of the lithium hydroxide that is added continues to stir 3～6 hours in the preparation of 2: 3 ratio of lithium vanadium mol ratio, obtains finely dispersed colloidal sol;
(3) gained colloid in the step (1) is evenly closed by a certain percentage with step (2) gained colloidal sol respectively, institute's doped metal ion is 0.1～10: 100 with respect to the molar ratio of vanadium;
(4) resulting gluey slurry in the step (3) is carried out spraying drying, use the peristaltic pump charging, speed is 10-20mL/min, under 0.1Mpa, produce atomizing, the control air inlet temperature is 300 ± 5 ℃, and temperature out is 100 ± 5 ℃, makes spherical powder, with the thermal treatment 3～6 hours under 300 ℃～400 ℃ conditions of the spherical powder of gained, get final product doping spherical lithium vanadate product.
Preparation spherical V 2 (V provided by the present invention
2O
5) and spherical lithium vanadate (Li
1+xV
3O
8) technology have the following advantages: technological process is simple; Adopted a kind of new method to prepare V
2O
5Colloidal sol; The V for preparing
2O
5And Li
1+xV
3O
8Product is spherical in shape, the bulk density height; The electrode specific capacity height of making; By the doping of other element (for example Co, Ni, Al), further improved the chemical property of material, have very big using value.
Embodiment
The invention provides a kind of with ammonium metavanadate (NH
4VO
3) prepare lithium ion battery anode material spherical vanadic anhydride (V for raw material
2O
5) and lithium vanadate (Li
1+xV
3O
8) and the technology of mixing, its implementation step is as follows:
(1) vanadic anhydride (V
2O
5) preparation of colloidal sol: take by weighing a certain amount of ammonium metavanadate (NH
4VO
3), in Muffle furnace, it is warming up to 750 ℃～1000 ℃, make its melting, be incubated after 1～3 hour, be preferably 2 hours, in the deionized water with its chilling vigorous stirring under room temperature, stir get final product after 1 hour V
2O
5Colloidal sol.
(2) drying of colloidal sol: the resulting gluey slurry of step (1) with pneumatic spray drying device drying, is adopted and the fluidized drying mode, and atomising device adopts the double-current method nozzle; Use the peristaltic pump charging, speed is 10-20mL/min, the orifice gas flow is controlled by compressed-air actuated pressure, under about 0.1Mpa, produce atomizing, the control temperature of inlet air is 300 ± 5 ℃, outlet is 100 ± 5 ℃, and outlet air separates emptying through the one-level vortex, makes after drying vanadic anhydride (V
2O
5) powder is spherical in shape.
Spherical lithium vanadate (Li provided by the present invention
1+xV
3O
8) preparation and doping process thereof, comprise following each step:
(1) preparation of vanadic anhydride colloidal sol: take by weighing a certain amount of ammonium metavanadate, in Muffle furnace, it is warming up to 750 ℃～1000 ℃, is incubated after 1～3 hour, be preferably 2 hours, in the deionized water with its chilling vigorous stirring under room temperature, stir get final product after 1 hour V
2O
5Colloidal sol;
(2) adding of lithium: at the V of step (1) gained
2O
5(amount of the LiOH that adds is in Li: the preparation of 2: 3 ratio of V mol ratio), continue to stir 3～6 hours, obtain finely dispersed colloidal sol to add lithium hydroxide (LiOH) solution in the colloidal sol;
(3) drying of colloidal sol: the resulting gluey slurry of step (2) with pneumatic spray drying device drying, is adopted and the fluidized drying mode, and atomisation unit adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10-20mL/min, and the orifice gas flow produces atomizing by compressed-air actuated pressure-controlling under about 0.1Mpa, and the control air inlet temperature is 300 ± 5 ℃, and outlet is 100 ± 5 ℃, and outlet air is through the emptying of one-level cyclone separation.The gained powder is spherical in shape;
(4) heat treatment: the spherical powder of step (3) gained is namely obtained spherical Li 300 ℃～400 ℃ lower heat treatments after 4 hours
1+xV
3O
8Product.
(5) mix: by necessarily measuring ratio with cobalt nitrate (Co (NO
3)
2), nickel nitrate (Ni (NO
3)
2), aluminum nitrate (Al (NO
3)
3) solution mixes under stirring condition with NaOH (NaOH) solution respectively, stirs 2～4 hours under 20 ℃～40 ℃ temperature conditions, repeated centrifugation, washing are 3～6 times again, make respectively Co (OH)
2, Ni (OH)
2, Al (OH)
3Colloid, (metal ion of doping is 0.1～10 with respect to the molar ratio of vanadium: 100) mix, make doping spherical lithium vanadate (Li by (3), (4) step more by a certain percentage with gained colloid and step (2) gained colloidal sol
1+xV
3O
8) product.
Introduce embodiments of the invention below:
Embodiment one: take by weighing 20gNH
4VO
3Insert in the corundum crucible, in Muffle furnace, it was warming up to 850 ℃ of meltings in 3 hours, be incubated after 1 hour, make V in the deionized water of chilling vigorous stirring under room temperature
2O
5Colloidal sol, resulting gluey slurry adopts and the fluidized drying mode with pneumatic spray drying device drying, and atomising device adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10mL/min, and the orifice gas flow produces atomizing by compressed-air actuated pressure-controlling under about 0.1Mpa, and the control air inlet temperature is 300 ℃, and outlet is 100 ℃, and outlet air is through the emptying of one-level cyclone separation.The 80 ℃ of bakings in baking oven of spray-drying gained powder namely got spherical V in 2 hours
2O
5Product.The tap density that records this sample is 1.42lg/cm
3Take by weighing this sample of 36.8mg, with sample powder, acetylene black and the PTFE mixed with 8: 1: 1, be pressed into electrode slice, as anodal, make negative pole with the pure metal lithium sheet after vacuum-drying, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 287mAh/g.
Embodiment two: make V by embodiment one
2O
5Colloidal sol, (amount of the LiOH that adds is by Li: 2: 3 proportional arrangement of V mol ratio) to add LiOH solution again, continue to stir 4 hours, resulting gluey slurry carries out spray-drying by embodiment one and makes spherical powder, namely obtains spherical Li at 350 ℃ after through heat treatment in 4 hours
1+xV
3O
8The tap density that records this sample is 1.448g/cm
3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 227mAh/g.
Embodiment three: with the Co (NO of 17.1mL, 0.5mol/L
3)
2Solution mixes under stirring condition with the NaOH solution of 17.1mL, 1mol/L, 30 ℃ of lower stirrings 3 hours, centrifugal, washing repeats 5 times again, make Co (OH) colloid, this colloid is mixed with the colloidal sol that adds Li that makes by embodiment two, press the drying of embodiment two, heat treatment method makes the spherical Li that mixes Co again
1+xV
3O
8The tap density that records this sample is 1.463g/cm
3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 225mAh/g.
Embodiment four: the method by embodiment three makes the spherical Li that mixes Ni
1+xV
3O
8The tap density that records this sample is 1.457g/cm
3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 223mAh/g.
Embodiment five: the method by embodiment three makes the spherical Li that mixes Al
1+xV
3O
8The tap density that records this sample is 1.443g/cm
3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 219mAh/g.
Comparing embodiment one: take by weighing 10gNH
4VO
3Insert in the corundum crucible, 500 ℃ of heat treatments made V after 20 hours in Muffle furnace
2O
5Powder.The tap density that records this sample is 1.158g/cm
3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 237mAh/g.
The NaVO of comparing embodiment two: 0.5M
3Solution obtains V by acid-treated 732 type cationic ion-exchange resins
2O
5Colloidal sol behind the adding LiOH solution, forms gels with 60 ℃ of heating water baths, heat-treats by embodiment two and makes Li
1+xV
3O
8Sample.The tap density that records this sample is 1.384g/cm
3Identical with the anode formula of embodiment two, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 202mAh/g.
Comparing embodiment three: the condition by embodiment one makes V
2O
5Colloidal sol also adds LiOH solution, forms gel with 60 ℃ of heating water baths then, heat-treats by embodiment two and makes Li
1+xV
3O
8Sample.The tap density that records this sample is 0.888g/cm
3Identical with the anode formula of embodiment two, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 175mAh/g.
Comparing embodiment four: the condition by embodiment two makes dried spherical powder, and powder is obtained Li 500 ℃ of heat treatments after 4 hours
1+xV
3O
8Sample.The tap density that records this sample is 1.003g/cm
3Identical with the anode formula of embodiment one, recording this sample is 0.16mA/cm in current density
2Specific discharge capacity when discharging and recharging is 178mAh/g.
Claims (3)
1, a kind of preparation method of lithium ion battery anode material spherical Vanadium Pentoxide in FLAKES is characterized in that: this method comprises following each step successively:
(1) take by weighing a certain amount of ammonium meta-vanadate, in retort furnace, it be warming up to 750 ℃～1000 ℃ fusions, be incubated after 1～3 hour, in the deionized water with its chilling vigorous stirring under room temperature, get final product Vanadium Pentoxide in FLAKES colloidal sol;
(2) the resulting gluey slurry of step (1) is carried out spraying drying, use the peristaltic pump charging, speed is 10-20mL/min, under 0.1Mpa, produce atomizing, the control air inlet temperature is 300 ± 5 ℃, and temperature out is 100 ± 5 ℃, promptly makes spherical V 2 colloidal sol powder after drying.
2, a kind of preparation method of lithium ion battery anode material spherical lithium vanadate is characterized in that: comprise following each step successively:
(1) preparation of Vanadium Pentoxide in FLAKES colloidal sol: take by weighing a certain amount of ammonium meta-vanadate, in retort furnace, it be warming up to 750 ℃～1000 ℃ fusions, be incubated after 1～3 hour, in the deionized water with its chilling vigorous stirring under room temperature, get final product Vanadium Pentoxide in FLAKES colloidal sol.
(2) add lithium hydroxide solution in the Vanadium Pentoxide in FLAKES colloidal sol of step (1) gained, the amount of the lithium hydroxide that is added continues to stir 3～6 hours in the preparation of 2: 3 ratio of lithium vanadium mol ratio, obtains finely dispersed colloidal sol;
(3) atomization drying of colloidal sol: the resulting gluey slurry of step (2) is carried out spraying drying, use the peristaltic pump charging, speed is 10-20mL/min, under 0.1Mpa, produce atomizing, the control air inlet temperature is 300 ± 5 ℃, and temperature out is 100 ± 5 ℃, makes spherical powder;
(4) with the thermal treatment 3～6 hours under 300 ℃～400 ℃ conditions of the spherical powder of step (3) gained, promptly obtain spherical lithium vanadate product.
3, a kind of the prepared spherical lithium vanadate of claim 2 is carried out adulterated method, it is characterized in that: this method comprises following each step successively:
(1) mol ratio by Xiao Suangu and sodium hydroxide is 1: 2, the mol ratio of nickelous nitrate and sodium hydroxide is 1: 2, aluminum nitrate and the mol ratio of sodium hydroxide are that 1: 3 metering mixes under agitation condition with sodium hydroxide solution respectively than with Xiao Suangu, nickelous nitrate or aluminum nitrate solution, under 20 ℃～40 ℃ temperature condition, stirred 2～4 hours, after repeated centrifugation, the washing, make cobaltous hydroxide, nickel hydroxide, alumine hydroxide colloid respectively again;
(2) add lithium hydroxide solution in Vanadium Pentoxide in FLAKES colloidal sol, the amount of the lithium hydroxide that is added continues to stir 3～6 hours in the preparation of 2: 3 ratio of lithium vanadium mol ratio, obtains finely dispersed colloidal sol;
(3) with gained colloid in the step (1) respectively with step (2) gained colloidal sol uniform mixing by a certain percentage, adulterated metal ion be 0.1～10: 100 with respect to the molar ratio of vanadium;
(4) resulting gluey slurry in the step (3) is carried out spraying drying, use the peristaltic pump charging, speed is 10-20mL/min, under 0.1Mpa, produce atomizing, the control air inlet temperature is 300 ± 5 ℃, and temperature out is 100 ± 5 ℃, makes spherical powder, with the thermal treatment 3～6 hours under 300 ℃～400 ℃ conditions of the spherical powder of gained, get final product doping spherical lithium vanadate product.
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