CN103199218B - A kind of method for preparing anode material of the lithium ion battery for portable game machine - Google Patents
A kind of method for preparing anode material of the lithium ion battery for portable game machine Download PDFInfo
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- CN103199218B CN103199218B CN201310118512.3A CN201310118512A CN103199218B CN 103199218 B CN103199218 B CN 103199218B CN 201310118512 A CN201310118512 A CN 201310118512A CN 103199218 B CN103199218 B CN 103199218B
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- 238000000034 method Methods 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 239000002086 nanomaterial Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007603 infrared drying Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract description 10
- 230000003044 adaptive effect Effects 0.000 abstract description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KKEZAVVOJGHSFU-UHFFFAOYSA-N diazanium dihydrogen phosphate Chemical compound [NH4+].[NH4+].OP(O)([O-])=O.OP(O)([O-])=O KKEZAVVOJGHSFU-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007921 spray Substances 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 method for preparing anode material of the lithium ion battery for portable game machine, it is characterized in that, the method comprises the steps:, and (1) prepares LiFePO4; (2) porous graphene material is prepared; (3) put into tube-type atmosphere furnace after above-mentioned precursor powder and graphene powder being sieved respectively, adopt two-part sintering, obtain LiFePO4/ grapheme composite positive electrode material.It is coated that this method adopts the grapheme material prepared of special process to carry out sintering to LiFePO4, while maintaining the high-octane density of LiFePO4, substantially improve the electric conductivity of positive electrode, make cyclical stability, charge rate all gets a promotion, and add the adaptive capacity to environment of battery.
Description
Technical field
The present invention relates to portable game machine field of power supplies, particularly relate to a kind of method for preparing anode material of the lithium ion battery for portable game machine.
Background technology
Along with the such as portable game machine such as PSP day by day universal, the requirement of people to the battery life of portable game machine is more and more higher, and the requirement reusing the life-span for battery is also more and more higher.
Lithium ion battery due to its energy density high, good cycle, has been widely used since its commercialization, and the battery also becoming portable game machine is first-selected.Portable game machine mainly needs consideration capacity, circulating battery stability (determining the useful life of battery), environmental adaptability and charge rate etc. when selecting battery.
The technical bottleneck of the realization of above-mentioned performance is mainly the preparation of the positive electrode of lithium ion battery.Anode material for lithium-ion batteries mainly contains LiCoO
2, LiNiO
2, LiMn
2o
4and LiFePO
4deng, the positive electrode used at present has respective shortcoming: LiCoO
2price high, charging voltage more than structural instability after 4.2V, deterioration of safety; LiNiO
2cycle performance bad, water absorption is strong, and storge quality is poor; LiMn
2o
4capacity low, high-temperature behavior is poor; LiFePO
4conductivity low, poor performance at low temperatures.Therefore, these anode material for lithium-ion batteries cannot meet the demand that lithium ion battery is high to specific capacity, the life-span is long, cost is low and environmental compatible aspect develops.Therefore, need to carry out modification to these positive electrodes.The approach of modification has two: one to be in positive electrode building-up process, mix other element to prepare doping vario-property material; Another is to prepare surface modifying material at the modifying surface of positive electrode.All there is coated uneven situation in above-mentioned two kinds of approach, thus cause coated after positive electrode capacity reduce and cycle performance decline, make shorter battery life.
Summary of the invention
In order to solve the problem, one object of the present invention is the method for preparing anode material providing a kind of lithium ion battery for portable game machine, when portable game machine is used, battery life is long, and useful life improves, and environment compatibility is good and charge rate is faster.
To achieve these goals, the invention discloses a kind of method for preparing anode material of the lithium ion battery for portable game machine, it is characterized in that, the method comprises the steps:
(1) synthesis of presoma
Lithium acetate, ferrous sulfate and ammonium phosphate ammonium phosphate are mixed, wherein, the mol ratio of the consumption of iron, lithium, phosphorus is: Fe: Li: P=1.0-1.2: 1.0-1.2: 1.0-1.1, after mixing, deionized water is dissolved in reaction vessel, be made into the mixed solution that concentration is 2-3mol/L, then take LiFePO
4the oxalic acid of Theoretical Mass 4-7% and get LiFePO
4the acetone of Theoretical Mass 4-5% adds in mixed solution, the reaction vessel that stirs is placed in 90-100 DEG C of water-bath, stir speed (S.S.) is 300-400r/min, and carrying out ultrasonic disperse, each ultrasonic time is 15-20 minute, is ultrasonicly spaced apart 10-15 minute, ultrasonic number of times is 3-5 time, then until mixed solution evaporate to dryness is obtained precursor, the presoma finally obtained is placed in infrared drying oven and carries out drying, after drying, presoma is taken out grind into powder;
(2) porous graphene material is prepared
Mass volume ratio (1-2) g:(2-3 by graphite powder and the concentrated sulfuric acid) graphite powder is distributed in the concentrated sulfuric acid by ml, hydrogen peroxide is added under stirring, the volume of added hydrogen peroxide is 2-3 times of the concentrated sulfuric acid, stir 1-2 minute, temperature rises to about 40-45 DEG C, adds concentrated sulfuric acid volume 2-3 times of distilled water, stirs 40-50 minute, through centrifugation, obtain graphite oxide nano material with after mass concentration 5-7% hydrochloric acid solution, distilled water and ethylene glycol cyclic washing;
By the graphite oxide nanomaterial solution of above-mentioned graphite oxide nano material preparation 15-20mg/mL, pouring the graphite oxide nano material aqueous solution into polytetrafluoroethylene is in the stainless steel cauldron of inner bag, wherein the volume ratio of the graphite oxide nano material aqueous solution and polytetrafluoroethylene is 3-4:5, stainless steel cauldron sealing is placed in air dry oven dry, then stainless steel cauldron is naturally cooled to room temperature, with the moisture content in filter paper draw solution, it is fully dry that the powder obtained is placed in vacuum drying chamber, obtains porous graphene material after ball milling;
(3) sintering obtains LiFePO
4/ grapheme composite positive electrode material
Tube-type atmosphere furnace is put into after above-mentioned precursor powder and graphene powder are crossed 200 mesh sieves respectively, wherein the mass ratio of Graphene and precursor powder is 3-5:100,600-700 DEG C is heated to heating rate 10-15 DEG C/min under reducing atmosphere, temperature retention time 5-8 hour, 800-900 DEG C is heated to again with heating rate 15-20 DEG C/min, insulation 10-12 hour, obtain LiFePO4/ grapheme composite positive electrode material, wherein argon gas and the hydrogen of reducing atmosphere to be volume flow ratio be 1:5-8.
Preferably, the power of described infrared drying oven is 500-800W in step (1), and irradiation time is 5-10 hour.
Preferably, the drying condition described in step (2) for react 8-10 hour under 200-250 ° of C condition.
Effect of the present invention is:
Coated by adopting the grapheme material prepared of special process to carry out sintering to LiFePO4, while maintaining the high-octane density of LiFePO4, substantially improve the electric conductivity of positive electrode, make cyclical stability, charge rate all gets a promotion, and add the adaptive capacity to environment of battery.When the lithium ion battery using this material to prepare is for portable game machine, the long flying power of battery of user can be met, outdoor adverse circumstances use and the demand in prolongation game machine (particularly the game machine of battery and fuselage one) useful life.
Embodiment
embodiment 1
Lithium acetate, ferrous sulfate and ammonium phosphate ammonium phosphate are mixed, wherein, the mol ratio of the consumption of iron, lithium, phosphorus is: Fe: Li: P=1.0: 1.0: 1.0, after mixing, in reaction vessel, be dissolved in deionized water, be made into the mixed solution that concentration is 2mol/L, then take LiFePO
4the oxalic acid of Theoretical Mass 4% and get LiFePO
4the acetone of Theoretical Mass 4% adds in mixed solution, the reaction vessel that stirs is placed in 90 DEG C of water-baths, stir speed (S.S.) is 300r/min, and carry out ultrasonic disperse, each ultrasonic time is 15 minutes, ultrasonicly be spaced apart 10 minutes, ultrasonic number of times is 3 times, then until mixed solution evaporate to dryness is obtained precursor, the presoma finally obtained is placed in infrared drying oven and carries out drying, the power of described infrared drying oven is 500W, and irradiation time is 10 hours, after drying, presoma is taken out grind into powder.
By the mass volume ratio 1g:2ml of graphite powder and the concentrated sulfuric acid, graphite powder is distributed in the concentrated sulfuric acid, hydrogen peroxide is added under stirring, the volume of added hydrogen peroxide is 2 times of the concentrated sulfuric acid, stir 1 minute, temperature rises to about 40 DEG C, adds concentrated sulfuric acid volume 2 times of distilled water, stirs 40 minutes, through centrifugation, obtain graphite oxide nano material with after mass concentration 5% hydrochloric acid solution, distilled water and ethylene glycol cyclic washing.
By the graphite oxide nano material aqueous solution of above-mentioned graphite oxide nano material preparation 15mg/mL, pouring the graphite oxide nano material aqueous solution into polytetrafluoroethylene is in the stainless steel cauldron of inner bag, wherein the volume ratio of the graphite oxide nano material aqueous solution and polytetrafluoroethylene is 3:5, stainless steel cauldron sealing is placed in air dry oven dry, then stainless steel cauldron is naturally cooled to room temperature, with the moisture content in filter paper draw solution, it is fully dry that the powder obtained is placed in vacuum drying chamber, described drying condition for react 8-10 hour under 200-250 ° of C condition, porous graphene material is obtained after ball milling.
Tube-type atmosphere furnace is put into after above-mentioned precursor powder and graphene powder are crossed 200 mesh sieves respectively, wherein the mass ratio of Graphene and precursor powder is 3:100,600 DEG C are heated to heating rate 10 DEG C/min under reducing atmosphere, temperature retention time 8 hours, 800 DEG C are heated to again with heating rate 15 DEG C/min, be incubated 12 hours, obtain LiFePO4/ grapheme composite positive electrode material, wherein argon gas and the hydrogen of reducing atmosphere to be volume flow ratio be 1:5.
embodiment 2
Lithium acetate, ferrous sulfate and ammonium phosphate ammonium phosphate are mixed, wherein, the mol ratio of the consumption of iron, lithium, phosphorus is: Fe: Li: P=1.2: 1.2: 1.1, after mixing, in reaction vessel, be dissolved in deionized water, be made into the mixed solution that concentration is 2-3mol/L, then take LiFePO
4the oxalic acid of Theoretical Mass 7% and get LiFePO
4the acetone of Theoretical Mass 5% adds in mixed solution, the reaction vessel that stirs is placed in 100 DEG C of water-baths, stir speed (S.S.) is 400r/min, and carry out ultrasonic disperse, each ultrasonic time is 20 minutes, ultrasonicly be spaced apart 15 minutes, ultrasonic number of times is 5 times, then until mixed solution evaporate to dryness is obtained precursor, the presoma finally obtained is placed in infrared drying oven and carries out drying, the power of described infrared drying oven is 800W, and irradiation time is 5 hours, after drying, presoma is taken out grind into powder.
By the mass volume ratio 2g:3ml of graphite powder and the concentrated sulfuric acid, graphite powder is distributed in the concentrated sulfuric acid, hydrogen peroxide is added under stirring, the volume of added hydrogen peroxide is 3 times of the concentrated sulfuric acid, stir 2 minutes, temperature rises to about 45 DEG C, adds concentrated sulfuric acid volume 3 times of distilled water, stirs 50 minutes, through centrifugation, obtain graphite oxide nano material with after mass concentration 7% hydrochloric acid solution, distilled water and ethylene glycol cyclic washing.
By the graphite oxide nano material aqueous solution of above-mentioned graphite oxide nano material preparation 20mg/mL, pouring the graphite oxide nano material aqueous solution into polytetrafluoroethylene is in the stainless steel cauldron of inner bag, wherein the volume ratio of the graphite oxide nano material aqueous solution and polytetrafluoroethylene is 4:5, stainless steel cauldron sealing is placed in air dry oven dry, then stainless steel cauldron is naturally cooled to room temperature, with the moisture content in filter paper draw solution, it is fully dry that the powder obtained is placed in vacuum drying chamber, described drying condition is react 8 hours under 250 ° of C conditions, porous graphene material is obtained after ball milling.
Tube-type atmosphere furnace is put into after above-mentioned precursor powder and graphene powder are crossed 200 mesh sieves respectively, wherein the mass ratio of Graphene and precursor powder is 5:100,700 DEG C are heated to heating rate 15 DEG C/min under reducing atmosphere, temperature retention time 5 hours, 900 DEG C are heated to again with heating rate 20 DEG C/min, be incubated 10 hours, obtain LiFePO
4/ grapheme composite positive electrode material, wherein argon gas and the hydrogen of reducing atmosphere to be volume flow ratio be 1:8.
comparative example
Phosphoric acid by 85 quality %: 10mol and citric acid monohydrate compound: 2mol is dissolved into distilled water: in 2000g, iron powder (JFE Steel Co., Ltd system is added in this mixed solution, oxygen content: 0.68 quality %, average grain diameter: 80 μm, apparent density: 3.18g/cm
3): 10mol, in liquid temperature: 25 ~ 30 DEG C, carry out stirring under air atmosphere while make it react one day.Then, the aqueous solution added containing lithium hydroxide: 10mol prepares the precursor of LiFePO4, use spray dryer (great river former chemical industry mechanism FOC16) in inlet temperature: carry out drying to this precursor under the condition of 200 DEG C, the average grain diameter obtaining being observed by SEM is about the dried powder of 30 μm.This dried powder is implemented to the once calcining of 400 DEG C × 5 hours in stream of nitrogen gas, then in a whole calcined material, add ascorbic acid: 40g as carbon source, and uses ball milling to carry out case of wet attrition, mixing.After the drying of gained mixture, in stream of nitrogen gas, implement the secondary clacining of 600 DEG C × 10 hours, finally sieve with sieve aperture 75 μm, prepare LiFePO4.
By embodiment one, two and comparative example products therefrom, be that 90:5:5 mixes according to the mass ratio of active material, conductive carbon black, binding agent Kynoar (PVDF) three, thickness is become to be about the electrode film of 0.15mm with wet film preparing device film, 120 DEG C of dryings 24 hours under vacuo, cut electrode slice with slicing machine, weigh and the quality of accurate calculated activity material.Using metal lithium sheet as to electrode and reference electrode, Clegard2500 makes barrier film, 1mol/LLiPF
6eC+DMC (volume ratio 1:1) solution be electrolyte, in the glove box being full of argon gas, be assembled into PSP wildcard battery.Then will preparation its chemical property of battery testing: after tested this embodiment one with two material compared with the material of comparative example, first discharge specific capacity improves more than 40-45%, and cycle life improves more than 1.5 times, and charge rate improves more than 2 times.
Claims (2)
1. for a method for preparing anode material for the lithium ion battery of portable game machine, it is characterized in that, the method comprises the steps:
(1) synthesis of presoma
Lithium acetate, ferrous sulfate and ammonium phosphate are mixed, wherein, the mol ratio of the consumption of iron, lithium, phosphorus is: Fe: Li: P=1.0-1.2: 1.0-1.2: 1.0-1.1, after mixing, deionized water is dissolved in reaction vessel, be made into the mixed solution that concentration is 2-3mol/L, then take LiFePO
4the oxalic acid of Theoretical Mass 4-7% and get LiFePO
4the acetone of Theoretical Mass 4-5% adds in mixed solution, the reaction vessel that stirs is placed in 90-100 DEG C of water-bath, stir speed (S.S.) is 300-400r/min, and carrying out ultrasonic disperse, each ultrasonic time is 15-20 minute, is ultrasonicly spaced apart 10-15 minute, ultrasonic number of times is 3-5 time, then until mixed solution evaporate to dryness is obtained precursor, the presoma finally obtained is placed in infrared drying oven and carries out drying, after drying, presoma is taken out grind into powder;
(2) porous graphene material is prepared
Mass volume ratio (1-2) g:(2-3 by graphite powder and the concentrated sulfuric acid) graphite powder is distributed in the concentrated sulfuric acid by ml, hydrogen peroxide is added under stirring, the volume of added hydrogen peroxide is 2-3 times of the concentrated sulfuric acid, stir 1-2 minute, temperature rises to 40-45 DEG C, adds concentrated sulfuric acid volume 2-3 times of distilled water, stirs 40-50 minute, through centrifugation, obtain graphite oxide nano material with after mass concentration 5-7% hydrochloric acid solution, distilled water and ethylene glycol cyclic washing;
By the graphite oxide nano material aqueous solution of above-mentioned graphite oxide nano material preparation 15-20mg/mL, pouring the graphite oxide nano material aqueous solution into polytetrafluoroethylene is in the stainless steel cauldron of inner bag, wherein the volume ratio of the graphite oxide nano material aqueous solution and polytetrafluoroethylliner liner is 3-4:5, stainless steel cauldron sealing is placed in air dry oven dry, drying condition for react 8-10 hour under 200-250 ° of C condition, then stainless steel cauldron is naturally cooled to room temperature, with the moisture content in filter paper draw solution, it is fully dry that the powder obtained is placed in vacuum drying chamber, porous graphene material is obtained after ball milling,
(3) sintering obtains LiFePO
4/ grapheme composite positive electrode material
Tube-type atmosphere furnace is put into after above-mentioned precursor powder and graphene powder are crossed 200 mesh sieves respectively, wherein the mass ratio of Graphene and precursor powder is 3-5:100,600-700 DEG C is heated to heating rate 10-15 DEG C/min under reducing atmosphere, temperature retention time 5-8 hour, 800-900 DEG C is heated to again with heating rate 15-20 DEG C/min, insulation 10-12 hour, obtains LiFePO
4/ grapheme composite positive electrode material, wherein argon gas and the hydrogen of reducing atmosphere to be volume flow ratio be 1:5-8.
2. the method for claim 1, is characterized in that, the power of described infrared drying oven is 500-800W in step (1), and irradiation time is 5-10 hour.
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| CN201310118512.3A CN103199218B (en) | 2013-04-08 | 2013-04-08 | A kind of method for preparing anode material of the lithium ion battery for portable game machine |
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| CN105449213B (en) * | 2015-12-29 | 2018-04-27 | 哈尔滨工业大学 | A kind of anode material for lithium-ion batteries of porous graphene coating modification and preparation method thereof |
| CN105655559A (en) * | 2016-01-19 | 2016-06-08 | 深圳市沃特玛电池有限公司 | Lithium ion battery and preparation method thereof |
| CN106856240B (en) * | 2017-01-06 | 2020-03-24 | 中昕（福建）石墨烯科技有限公司 | Graphene power battery with excellent performance and preparation method thereof |
| CN107275597B (en) * | 2017-05-27 | 2020-02-14 | 广东烛光新能源科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN107834054B (en) * | 2017-12-19 | 2020-11-13 | 宁波高新区锦众信息科技有限公司 | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery |
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| CN101404328A (en) * | 2008-10-30 | 2009-04-08 | 昆明理工大学 | Preparation method of positive electrode material of lithium ion cell |
| CN101800310B (en) * | 2010-04-02 | 2013-02-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing graphene-doped anode material for lithium-ion batteries |
| CN103022460A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing lithium titanate carbon composite material |
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