CN103066278B - LiFePO 4 material of the coated vanadium doping of tin oxide and preparation method thereof - Google Patents

LiFePO 4 material of the coated vanadium doping of tin oxide and preparation method thereof Download PDF

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CN103066278B
CN103066278B CN201210437310.0A CN201210437310A CN103066278B CN 103066278 B CN103066278 B CN 103066278B CN 201210437310 A CN201210437310 A CN 201210437310A CN 103066278 B CN103066278 B CN 103066278B
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lithium
preparation
tin
tin oxide
mixture
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CN103066278A (en
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姜应律
蔡若愚
杨国凯
钟雅文
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Zhejiang Narada Power Source Co Ltd
Hangzhou Nandu Power Technology Co Ltd
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HANGZHOU NANDU ENERGY TECHNOLOGY Co Ltd
HANGZHOU NARADA BATTERY CO Ltd
Zhejiang Narada Power Source Co Ltd
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    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses anode material for lithium-ion batteries tin oxide coated LiFePO 4 for lithium ion batteries material and preparation method thereof, it adopts surface coating technology at active substance of lithium ion battery anode Surface coating one deck sull, mix vanadium and carry out ion diffuse modification, obtain LiFe by single step reaction synthesis 1-xv xpO 4ySnO(0.01≤x≤0.05,0.005≤y≤0.05) lithium iron phosphate positive material.The present invention obtains Stability Analysis of Structures, lithium iron phosphate positive material that electro-chemical activity is high by a kind of simple method, to overcome the technological deficiency of existing LiFePO4 poorly conductive, tap density low and high temperature stable circulation difference, in cost control, Simplified flowsheet, discharge capacity, cyclicity, large current discharging capability etc., there is stronger competitive advantage, thus prepare the anode composite material of lithium ion battery with high-performance height cyclical stability.

Description

LiFePO 4 material of the coated vanadium doping of tin oxide and preparation method thereof
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, be specifically related to be anode material for lithium-ion batteries and preparation method.
Background technology
Along with the develop rapidly of electrokinetic cell and energy-storage battery industry, people had higher requirement to the useful life of lithium ion battery and security performance.Other traditional positive electrode relatively, the advantages such as LiFePO 4 material has good cycle and security performance is high, abundant raw material source, cheap, environmental protection, arouse widespread concern and study, therefore become the positive electrode of power and energy storage lithium ion battery first-selection.But LiFePO 4 material still also exists high temperature circulation capacity attenuation, electronic conductivity and the problem such as ion diffusion rates is low, thus constrain further developing and applying of LiFePO 4 material and battery thereof.For overcoming the above problems, Chinese scholars has carried out surface finishing work, as at Surface coating one deck carbon of positive active material or metal oxide, to improve the state of interface of electrolyte and positive active material, suppress negative reaction between the two, reach the object improving cyclical stability under high temperature.
The LiFePO4 generally commercially produced, in order to improve electronic conductivity and the lithium ion diffusion rate of LiFePO 4 material, have employed carbon coated conductive agent, if number of patent application is the application for a patent for invention of 2007101556819.7.Although this can improve the chemical property of material, but the specific area of LiFePO 4 material can be increased, reduce the tap density of material, not only have impact on the Physical Processing performance of material, also can reduce the volume energy density of battery simultaneously, affect the consistency of battery performance.Meanwhile, the stripping of micro Fe element is the reason (Jin H F, Liu Z, et al.Journal of Power Sources, 2009, l89:445-448) causing LiFePO 4 material high temperature circulation capacity attenuation.Because LiFePO 4 material is at LiPF 6in electrolyte system, meeting is the stripping Fe by the acid etching of HF in electrolyte inevitably 2+, the Fe of stripping 2+can be reduced into Fe and be deposited on graphite cathode on the surface, it not only can hinder Li +deintercalation, the misgrowth of catalysis negative pole SEI film, and even can generate Fe dendrite, thus cause material at high temperature Capacity fading is to meet the instructions for use of electrokinetic cell to positive electrode like this.
Summary of the invention
First object of the present invention is to provide a kind of novel anode material for lithium-ion batteries, and it is the composite ferric lithium phosphate material LiFe of the coated vanadium doping of tin oxide 1-xv xpO 4ySnO 2; Wherein 0.01≤x≤0.05,0.005≤y≤0.05.The present invention adopts surface coating technology at active substance of lithium ion battery anode Surface coating one deck sull, overcome the technological deficiency of existing LiFePO4 poorly conductive, tap density low and high temperature stable circulation difference, it has high-performance height cyclical stability.
Described lithium iron phosphate particles particle diameter is 2-15 μm.
The thickness of the tin oxide coated LiFePO 4 for lithium ion batteries Surface coating film of vanadium doping is 4-10nm.
Another technical problem to be solved of the present invention is to provide a kind of preparation method of above-mentioned anode material for lithium-ion batteries, and for this reason, the present invention adopts following technical scheme:
(1) take doping vfanadium compound and tin source compound, respectively, be mixed in solvent;
(2), step (1) gained solution is fully mixed according to the mol ratio of Li:Fe:V:P:Sn=x:1-y:y:1:z with source of iron, lithium source, phosphoric acid root timber material, ball milling, drying; 1.0≤x≤1.05,0.01≤y≤0.05,0.005≤z≤0.05
(3), step (2) is obtained product essence fragmentation after in protective atmosphere with 2-5 othe heating rate of C/min is heated to 650-800 oc, insulation 3-15 hour, is cooled to room temperature, obtains iron phosphate powder;
(4), the product of step (3) gained is obtained after air-flow crushing the tin oxide coated lithium iron phosphate composite of vanadium doping.
The mixture of a kind of in the optional lithium hydroxide of the lithium salts used in the present invention, lithium acetate, lithium carbonate, lithium nitrate or any two kinds.
The source of iron used in the present invention is ferrous oxalate, the mixture of a kind of in ferric nitrate, iron hydroxide, iron oxide or any two kinds.
The phosphoric acid root timber material used in the present invention is phosphorus pentoxide, phosphoric acid; One or more mixtures of ammonium dihydrogen phosphate, polyphosphoric acids.
Use in the present invention containing the compound of vanadium be vanadic oxide, two kinds of mixtures of vanadium trioxide, ammonium metavanadate a kind of or any two kinds.
Tin source compound used in the present invention is the mixture of butter of tin, tin oxychloride, stannous oxide a kind of or any two kinds.
The solvent that the present invention uses is ethanol, one or more in acetone, deionized water.
The protective atmosphere used in the present invention can be nitrogen, argon gas, nitrogen and hydrogen mixture or argon hydrogen gaseous mixture.
Technical conceive of the present invention is the ion diffuse being improved lithium ion battery anode material lithium iron phosphate by vanadium doping, and coated fin oxide condutire agent improves the electron conduction of LiFePO4, the discharge capacity improving material with
High rate performance.The coated LiFePO 4 material that can reduce of tin oxide is at LiPF 6in electrolyte system because of acid etching Fe 2+phenomenon, thus improve the high temperature cyclic performance of material.
The present invention is by Li source compound, Fe source compound, phosphoric acid root timber material, vanadium source compound, the mixing of tin source compound, and disposable vanadium source has prepared the tin oxide coated lithium iron phosphate composite of novel vanadium doping.Prepared material has higher jolt ramming and compacted density, high conductivity, greatly improves high rate performance and the high temperature cyclic performance of composite material.The tap density of composite ferric lithium phosphate material of the present invention is 1.2g/cm 3, compacting is 2.3-2.5g/cm 3, in electro-chemical test, button cell is with 0.2C(34mA/g) multiplying power to carry out reversible capability of charging and discharging be 156mAh/g, carry out reversible capability of charging and discharging for 102mAh/g with 10C multiplying power (1700mA/g).Make the full battery battery core of 1Ah, with 1C(1000mA at 55 DEG C) circulation is after 500 weeks, and capability retention is 83.6%.Simple, with low cost with the tin oxide coated lithium iron phosphate composite preparation method technique of vanadium doping, the anode material for lithium-ion batteries that high power capacity, low internal resistance, high magnification, cycle performance are outstanding can be obtained, there is the value of practical application, be applicable to industrialization large-scale production.
Accompanying drawing explanation
Fig. 1 is the composite ferric lithium phosphate material stereoscan photograph of the coated vanadium doping of tin oxide prepared by the embodiment of the present invention 1.
Fig. 2 is the composite ferric lithium phosphate material transmission electron microscope photo of the coated vanadium doping of tin oxide prepared by the embodiment of the present invention 1.
Fig. 3 is the composite ferric lithium phosphate material button cell 0.2C high rate performance test of the coated vanadium doping of tin oxide prepared by the embodiment of the present invention 1.
Fig. 4 is the composite ferric lithium phosphate material button cell high rate capability test result figure of the coated vanadium doping of tin oxide prepared by the embodiment of the present invention 1.
Fig. 5 is the composite ferric lithium phosphate material full battery high-temperature cycle performance test result figure of the coated vanadium doping of tin oxide prepared by the embodiment of the present invention 1.
Embodiment
Embodiment 1
By 4.7g ammonium metavanadate (NH 4vO 3) and 21g butter of tin (SnCl 4), be dissolved in 100mL water, form solution; The solution obtained and 360g ferrous oxalate, 230g ammonium dihydrogen phosphate and 74 grams of lithium carbonates are fully mixed, ball milling, oven dry, obtain presoma material; Presoma material is carried out essence fragmentation and be heated to 680 DEG C with the heating rate of 2 DEG C/min under nitrogen protective atmosphere; be incubated 12 hours, with stove cooling, obtain LiFePO4 product; after air-flow crushing, obtain the LiFePO 4 material of the coated vanadium doping of tin oxide.
The tin oxide coated lithium iron phosphate composite of the vanadium doping obtained is carried out scanning electron microscopic observation, and result is as shown in Fig. 1.As seen from Figure 1, the tin oxide coated lithium iron phosphate composite primary particle of the vanadium doping of gained is at 200-300nm, and second particle is at about 3 μm.Sample is carried out high-resolution-ration transmission electric-lens (HR-TEM) to observe, structure as shown in Figure 2.As can be seen from Figure 2, the tin oxide coated lithium iron phosphate composite of the vanadium doping of gained is monocrystalline, and Surface coating layer thickness is about about 5nm, and distributes at LiFePO 4 material surface uniform.
The tin oxide coated lithium iron phosphate composite of the vanadium doping obtained is carried out button cell test, positive electrode active material powder, conductive agent acetylene black, adhesive PVDF, be the ratio mixing of 80:14:6 in mass ratio, negative pole is metal lithium sheet, barrier film is Celgard2400 microporous barrier, and electrolyte is 1M LiPF 6/ EC+EMC+DEC (volume ratio 1:1:1).Test under the different charging and discharging currents condition of 2-4.0V scope, the results are shown in accompanying drawing 3 and Fig. 4, as can be seen from Fig. 3 and Fig. 4, composite ferric lithium phosphate material polarization prepared by the method is very little, it is 156mAh/g that multiplying power 0.2C(34mA/g) carries out reversible capability of charging and discharging, under 2C multiplying power (340mA/g), reversible capacity is 144 mAh/g, carries out reversible capability of charging and discharging for 102mAh/g with 10C multiplying power (1700mA/g).
1Ah Soft Roll made by full battery, 92% active positive electrode material, 2%SP, 2%KS-6 conductive agent, 4%PVDF binding agent, the two-sided 320g/cm of surface density 2, compacted density 2.35g/cm 3, negative pole is Delanium (95.3%), SP(1.1%), CMC(1.1%), SBR(2.5%) and, water prescription.Electrolyte adopts FE-4.Battery leaves standstill 15min, under the condition of ambient temperature 55 DEG C, with 1C current discharge to final voltage 2V after charging to 3.8V by regulation standard.With 1C(1000mA at 55 DEG C) circulation is after 500 weeks, and capability retention is 83.6%.
Embodiment 2
By 3.64g vanadic oxide (V 2o 5) and 21g butter of tin (SnCl 4), be dissolved in 100mL water, form solution; The solution obtained and 160g iron oxide, 230g ammonium dihydrogen phosphate and 74 grams of lithium carbonates are fully mixed, ball milling, oven dry obtain presoma material, under nitrogen nitrogen atmosphere, 730 DEG C are heated to the heating rate of 3 DEG C/min after essence fragmentation, be incubated 8 hours, cool with stove, obtain LiFePO4 product, after air-flow crushing, obtain the LiFePO 4 material of the coated vanadium doping of tin oxide.
Embodiment 3
By 3g vanadium trioxide (V 2o 3) and 10.8g stannous oxide (SnO), use dissolving oxalic acid in 100mL water, form solution; The solution obtained and 156g iron oxide, 230g ammonium dihydrogen phosphate and 74 grams of lithium carbonates are fully mixed, ball milling, oven dry obtain presoma material, after smart fragmentation under nitrogen and hydrogen mixture atmosphere with 3
DEG C/heating rate of min is heated to 730 DEG C, is incubated 8 hours, and with stove cooling, obtain LiFePO4 product, after air-flow crushing, obtain the LiFePO 4 material of the coated vanadium doping of tin oxide.
Embodiment 4
By 11.7g ammonium metavanadate (NH 4vO 3) and 31.5g butter of tin (SnCl 4), be dissolved in 100mL water, form solution; The solution obtained and 207.3g iron hydroxide, 230.6g phosphoric acid and 135.96 grams of lithium acetates are fully mixed, ball milling, oven dry obtain presoma material, under argon hydrogen mixed atmosphere, 710 DEG C are heated to the heating rate of 3 DEG C/min after essence fragmentation, be incubated 10 hours, cool with stove, obtain LiFePO4 product, after air-flow crushing, obtain the LiFePO 4 material of the coated vanadium doping of tin oxide.
Embodiment 5
By 11.7g ammonium metavanadate (NH 4vO 3) and 28g tin oxychloride (SnOCl 2), be dissolved in 150mL ethanol, form solution; The solution obtained and 775.68g ferric nitrate, 230.6g phosphoric acid and 84 grams of lithium hydroxides are fully mixed, ball milling, oven dry obtain presoma material, under nitrogen and hydrogen mixture atmosphere, 660 DEG C are heated to the heating rate of 2 DEG C/min after essence fragmentation, be incubated 12 hours, cool with stove, obtain LiFePO4 product, after air-flow crushing, obtain the LiFePO 4 material of the coated vanadium doping of tin oxide.
Embodiment 6
By 5g vanadium trioxide (V 2o 3) and 31.5g tin oxychloride (SnOCl 2), be dissolved in 150mL acetone, form solution; The solution obtained and 178g ferrous oxalate, 230.6g phosphoric acid and 84 grams of lithium hydroxides are fully mixed, ball milling, oven dry obtain presoma material; under argon shield atmosphere, 660 DEG C are heated to the heating rate of 2 DEG C/min after essence fragmentation; be incubated 12 hours; cool with stove; obtain LiFePO4 product; after air-flow crushing, obtain the LiFePO 4 material of the coated vanadium doping of tin oxide.

Claims (9)

1. a preparation method for anode material for lithium-ion batteries, is characterized in that described anode material for lithium-ion batteries is the LiFePO 4 material LiFe of the coated vanadium doping of tin oxide 1-xv xpO 4ySnO; Wherein 0.01≤x≤0.05,0.005≤y≤0.05, described preparation method comprises the steps:
(1) take doping vfanadium compound and tin source compound, respectively, be mixed in solvent;
(2), step (1) gained solution is fully mixed according to the mol ratio of Li:Fe:V:P:Sn=x:1-y:y:1:z with source of iron, lithium source, phosphoric acid root timber material, ball milling, drying, 1.0≤x≤1.05,0.01≤y≤0.05,0.005≤z≤0.05;
(3), step (2) is obtained product essence fragmentation after in protective atmosphere with 2-5 othe heating rate of C/min is heated to 650-800 oc, insulation 3-15 hour, is cooled to room temperature, obtains iron phosphate powder; Described protective atmosphere is nitrogen, argon gas, nitrogen and hydrogen mixture or argon hydrogen gaseous mixture;
(4) product of step (3) gained is obtained after air-flow crushing the composite ferric lithium phosphate material of the coated vanadium doping of tin oxide.
2. preparation method as claimed in claim 1, is characterized in that, the mixture of a kind of in the optional lithium hydroxide of lithium salts that step (2) uses, lithium acetate, lithium carbonate, lithium nitrate or any two kinds.
3. preparation method as claimed in claim 1, is characterized in that, the source of iron that step (2) uses is ferrous oxalate, the mixture of a kind of in ferric nitrate, iron hydroxide, iron oxide or any two kinds.
4. preparation method as claimed in claim 1, is characterized in that, the phosphoric acid root timber material that step (2) uses is phosphorus pentoxide, phosphoric acid; One or more mixtures of ammonium dihydrogen phosphate, polyphosphoric acids.
5. preparation method as claimed in claim 1, is characterized in that, the compound containing vanadium that step (1) uses is vanadic oxide, the mixture of vanadium trioxide, ammonium metavanadate a kind of or any two kinds.
6. preparation method as claimed in claim 1, is characterized in that, the tin source compound that step (1) uses is butter of tin, the mixture of tin oxychloride, stannous oxide a kind of or any two kinds.
7. preparation method as claimed in claim 1, is characterized in that, the solvent that step (1) uses is ethanol, one or more in acetone, deionized water.
8. preparation method as claimed in claim 1, it is characterized in that, described lithium iron phosphate particles particle diameter is 2-15 μm.
9. preparation method as claimed in claim 1, is characterized in that the thickness of the tin oxide coated LiFePO 4 for lithium ion batteries Surface coating film of vanadium doping is 4-10nm.
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CN107068995B (en) * 2017-02-15 2019-12-27 浙江大学 In-situ precipitated oxide coated lithium ion battery positive electrode material and preparation method and application thereof
CN107146877B (en) * 2017-05-03 2021-02-19 武汉理工大学 Preparation method of fluoxaphosphate lithium ion battery material, positive plate and lithium ion battery
CN107425187B (en) * 2017-07-27 2018-05-29 刘晓娟 LiFePO 4 material of antimony-chromium doped stannum oxide cladding and preparation method thereof
CN108455551A (en) * 2018-02-01 2018-08-28 厦门劦能科技有限公司 A kind of manufacturing method of lithium iron phosphate positive material and lithium secondary battery using the positive electrode
CN110380043A (en) * 2019-08-14 2019-10-25 湖南金富力新能源股份有限公司 The positive electrode and preparation method thereof of fluoro- phosphorus doping tin oxide coating modification

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CN101924198A (en) * 2010-06-12 2010-12-22 河北金力新能源材料科技有限公司 Positive pole material of lithium ion battery and preparation method thereof
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