CN101937986A - Vanadium-lithium phosphate composite material for positive electrode of lithium ion battery and preparation method thereof - Google Patents

Vanadium-lithium phosphate composite material for positive electrode of lithium ion battery and preparation method thereof Download PDF

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Publication number
CN101937986A
CN101937986A CN2010102687212A CN201010268721A CN101937986A CN 101937986 A CN101937986 A CN 101937986A CN 2010102687212 A CN2010102687212 A CN 2010102687212A CN 201010268721 A CN201010268721 A CN 201010268721A CN 101937986 A CN101937986 A CN 101937986A
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lithium ion
composite material
ion battery
lithium
mixture
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CN101937986B (en
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涂江平
乔彦强
王秀丽
张文魁
孙建平
黄辉
程丽娟
缪东栋
张官富
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ZHEJIANG GUSHEN ENERGY TECHNOLOGY Co Ltd
Zhejiang University ZJU
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ZHEJIANG GUSHEN ENERGY TECHNOLOGY Co Ltd
Zhejiang University ZJU
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    • 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

Abstract

The invention discloses a vanadium-lithium phosphate composite material for a positive electrode of a lithium ion battery. The material is powder which is formed by coating surface of Li3V2(PO4)3 with multi-wall carbon nanotube-modified amorphous carbon in situ; and the material comprises 95 to 98 mass percent of Li3V2(PO4)3 and 2 to 5 mass percent of carbon. A preparation method of the material comprises the following steps of: mixing Li2CO3, NH4H2PO4 and NH4VO3 serving as raw materials according to a stoichiometric ratio of the Li3V2(PO4)3; adding the multi-wall carbon nanotubes and polyvinyl alcohol into the mixture; adding anhydrous alcohol into the mixture and mixing the mixture by ball milling on a ball mill; and calcining the mixture in an argon atmosphere to obtain the material. The vanadium-lithium phosphate composite material of the invention is used for the positive electrode of the lithium ion battery, has the advantages of high charging and discharging capacity, high cyclical stability, superior high-rate performance and high material conductivity and is suitable for providing a power energy source for portable electric tools, electric motorcycles, electric automobiles and the like.

Description

Be used for phosphoric acid vanadium lithium composite material of lithium ion cell positive and preparation method thereof
Technical field
The present invention relates to the lithium ion battery field, especially a kind of anode material for lithium-ion batteries that can be used for high power charging-discharging and preparation method thereof.
Background technology
Lithium-ions battery is as a kind of high performance green power supply of filling, in various portable type electronic products and communication tool, be used widely in recent years, to progressively be developed as the electrical source of power of electric automobile, be developed thereby promote its direction to safety, environmental protection, low cost and high-energy-density.The fast development of novel high-energy chemical power source technology is had higher requirement to battery material, and high-energy-density, high power density, low cost, environment amenable novel battery material are the present and following research emphasis.
Therefore; choose selecting for use of additive from raw-material; to parameters Optimization, the researcher in battery technology field has carried out a large amount of trials and exploration from the protection of production environment, and purpose is at the high-rate charge-discharge capability that guarantees to improve on the normal basis of using of battery lithium ion battery.With Li 3V 2(PO 4) 3Be the vanadium phosphate compounds of the representative characteristics such as environmental protection, security performance are good because having, Stability Analysis of Structures, chemical property are better, become the focus that people in recent years study.But be separated by far owing to the reason metal ion of crystal structure, make that the mobility of electronics is low in the material, Li 3V 2(PO 4) 3Electronic conductivity be 2 * 10 -7S/cm, Li +Diffusion coefficient in solid phase is 10 -9～10 -13Cm 2/ s, these shortcomings have greatly limited Li 3V 2(PO 4) 3Chemical property.
Common solution is to coat or bulk phase-doped material is carried out modification to improve electronic conductivity by carbon.It is the carbon source precursor that the researcher generally adopts high specific surface carbon, glucose, sucrose or maltose etc., preparation Li 3V 2(PO 4) 3/ C composite; But the material property that usually obtains can not solve the high-rate charge-discharge capability of lithium ion battery well.MWCNTs has extraordinary conductivity, its along tubular axis to electronic conductivity be (1～4) * 10 2S cm -1, conductivity perpendicular to axial direction is 5～25S cm -1Material analysis shows that MWCNTs can obviously improve Li 3V 2(PO 4) 3The electric conductivity of/C, cycle performance and high rate performance will obviously be better than Li 3V 2(PO 4) 3/ C electrode material.
Summary of the invention
The purpose of this invention is to provide a kind of have a high power charging-discharging be used for phosphoric acid vanadium lithium composite material of lithium ion cell positive and preparation method thereof.
Phosphoric acid vanadium lithium composite for lithium ion cell positive of the present invention is the amorphous carbon original position coating Li by the multi-walled carbon nano-tubes modification 3V 2(PO 4) 3The powder that the surface forms contains: 95%～98% Li by mass percentage 3V 2(PO 4) 3, 2%～5% carbon.
The particle diameter of powder is 200～600nm.
Be used for the preparation method of the phosphoric acid vanadium lithium composite material of lithium ion cell positive, its step is as follows:
Press Li 3V 2(PO 4) 3Stoichiometric proportion with raw material Li 2CO 3, NH 4H 2PO 4And NH 4VO 3Mix, add the multi-walled carbon nano-tubes (MWCNTs) and the polyvinyl alcohol (PVA) that account for raw material gross mass 10～30%, the weight ratio of multi-walled carbon nano-tubes and polyvinyl alcohol is 1: 1, add absolute ethyl alcohol after ball milling on the ball mill mixes, in 850 ℃ of calcining 10h, the amorphous carbon original position that obtains the multi-walled carbon nano-tubes modification coats Li in argon gas atmosphere 3V 2(PO 4) 3The powder that the surface forms.
The preparation of anode pole piece: with phosphoric acid vanadium lithium composite material and adhesive polyvinylidene fluoride (PVDF) and conductive black mixed by 91: 6: 3, add deionized water and stirring and become pasty state, evenly be coated in aluminium foil surface, then pole piece dried 12h down at 85 ℃.After the roll squeezer compacting, place vacuum drying oven again electrode slice, divide the positive plate that cuts into lithium ion battery in 90 ℃ of dry 8h.
The assembling of battery: the electrode slice of making is assembled into lithium ion battery as lithium ion cell positive and battery cathode sheet.Electrolyte is to contain 1mol/L LiPF 6DEC+EC (volume ratio DEC: EC=7: 3), barrier film polypropylene Celgard2300.The battery assembling process is finished in relative humidity is lower than 1% dry glove box.The battery that assembles carries out the constant current charge-discharge test after placing 12h, charging/discharging voltage is 3V～4.3V, circulates under 0.5C～10C charge-discharge magnification (rate of charge is identical with corresponding discharge-rate) in 25 ℃ ± 2 ℃ environment and measures reversible embedding lithium capacity, charge-discharge performance and the high-rate charge-discharge capability of lithium ion cell positive.
Advantage of the present invention:
Phosphoric acid vanadium lithium composite material of the present invention is used for lithium ion cell positive, charge/discharge capacity height, good cycling stability.The high rate capability excellence, material electric conductivity height.The lithium ion battery that uses this positive electrode to make has high-rate charge-discharge capability, has extended cycle life, capacity height, safe in utilization, environmental protection, with low cost; Being fit to provides power source to portable power tool, battery-operated motor cycle and electric automobile etc.The preparation method of multi-multiplying power charging-discharging lithium ion battery positive pole provided by the invention, technological operation is simple, is suitable for large-scale production.
Description of drawings
Fig. 1 is the cycle performance of phosphoric acid vanadium lithium composite material of the present invention under different charge-discharge magnifications.
Embodiment
Embodiment 1:
Press Li 3V 2(PO 4) 3Stoichiometric proportion with raw material Li 2CO 3, NH 4H 2PO 4And NH 4VO 3Mix, add the MWCNTs and the PVA that account for raw material gross mass 10%, the weight ratio of MWCNTs: PVA is 1: 1, adds 15ml absolute ethyl alcohol ball milling 10h on ball mill, and drum's speed of rotation is set to 350rpm.Raw material is put into tube furnace after taking out drying, and (air velocity is 80ml/min) obtains coating Li by the amorphous carbon original position of multi-walled carbon nano-tubes modification in 850 ℃ of calcining 10h in argon gas atmosphere 3V 2(PO 4) 3Powder (the Li that the surface forms 3V 2(PO 4) 3/ C), contain by mass percentage: 98% Li 3V 2(PO 4) 3, 2% carbon.
The product of gained shows to be Li through XRD analysis 3V 2(PO 4) 3, there is not dephasign, the particle diameter that can obtain product by SEM is at 200～600nm, and MWCNTs is evenly distributed between particle.
Li with the MWCNTs modification for preparing 3V 2(PO 4) 3/ C positive electrode mixes in 91: 6: 3 ratio with adhesive polyvinylidene fluoride (PVDF) and conductive carbon black as electrode active material, add deionized water and stirring and evenly become pasty state, evenly be coated in aluminium foil surface, then with pole piece oven dry 12h under 85 ℃.After the roll squeezer compacting, place vacuum drying oven again electrode slice, divide the positive plate that cuts into lithium ion battery in 90 ℃ of dry 8h.
The electrode slice of making is assembled into lithium ion battery as lithium ion cell positive and battery cathode sheet.Electrolyte is to contain 1mol/L LiPF 6DEC+EC (volume ratio DEC: EC=7: 3), barrier film polypropylene Celgard2300.The battery assembling process is finished in relative humidity is lower than 1% dry glove box.The battery that assembles carries out the constant current charge-discharge test after placing 12h, charging/discharging voltage is 3V～4.3V, circulates under 0.5C～10C charge-discharge magnification (rate of charge is identical with corresponding discharge-rate) in 25 ℃ ± 2 ℃ environment and measures reversible embedding lithium capacity, charge-discharge performance and the high-rate charge-discharge capability of lithium ion cell positive.
The discharge capacity of this routine lithium ion cell positive under different discharge-rates sees Table 1.
Embodiment 2:
Press Li 3V 2(PO 4) 3Stoichiometric proportion with raw material Li 2CO 3, NH 4H 2PO 4And NH 4VO 3Mix, add the MWCNTs and the PVA that account for raw material gross mass 20%, the weight ratio of MWCNTs: PVA is 1: 1, adds 15ml absolute ethyl alcohol ball milling 10h on ball mill, and drum's speed of rotation is set to 350rpm.Raw material is put into tube furnace after taking out drying, and (air velocity is 80ml/min) obtains the Li of MWCNTs modification in 850 ℃ of calcining 10h in argon gas atmosphere 3V 2(PO 4) 3/ C positive electrode contains: 96.5% Li by mass percentage 3V 2(PO 4) 3, 3.5% carbon.
The product of gained shows to be Li through XRD analysis 3V 2(PO 4) 3, there is not dephasign, the particle diameter that can obtain product by SEM is at 200～600nm, and MWCNTs is evenly distributed between particle.
Li with the MWCNTs modification for preparing 3V 2(PO 4) 3/ C positive electrode mixes in 91: 6: 3 ratio with adhesive polyvinylidene fluoride (PVDF) and conductive carbon black as electrode active material, add deionized water and stirring and evenly become pasty state, evenly be coated in aluminium foil surface, then with pole piece oven dry 12h under 85 ℃.After the roll squeezer compacting, place vacuum drying oven again electrode slice, divide the positive plate that cuts into lithium ion battery in 90 ℃ of dry 8h.
The electrode slice of making is assembled into lithium ion battery as lithium ion cell positive and battery cathode sheet.Electrolyte is to contain 1mol/L LiPF 6DEC+EC (volume ratio DEC: EC=7: 3), barrier film polypropylene Celgard2300.The battery assembling process is finished in relative humidity is lower than 1% dry glove box.The battery that assembles carries out the constant current charge-discharge test after placing 12h, charging/discharging voltage is 3V～4.3V, circulates under 0.5C～10C charge-discharge magnification (rate of charge is identical with corresponding discharge-rate) in 25 ℃ ± 2 ℃ environment and measures reversible embedding lithium capacity, charge-discharge performance and the high-rate charge-discharge capability of lithium ion cell positive
The discharge capacity of this routine lithium ion cell positive under different discharge-rates sees Table 1.
Embodiment 3:
Press Li 3V 2(PO 4) 3Stoichiometric proportion with raw material Li 2CO 3, NH 4H 2PO 4And NH 4VO 3Mix, add the MWCNTs and the PVA that account for raw material gross mass 30%, the weight ratio of MWCNTs: PVA is 1: 1, adds 15ml absolute ethyl alcohol ball milling 10h on ball mill, and drum's speed of rotation is set to 350rpm.Raw material is put into tube furnace after taking out drying, and (air velocity is 80ml/min) obtains the Li of MWCNTs modification in 850 ℃ of calcining 10h in argon gas atmosphere 3V 2(PO 4) 3/ C positive electrode contains: 95% Li by mass percentage 3V 2(PO 4) 3, 5% carbon.
The product of gained shows to be Li through XRD analysis 3V 2(PO 4) 3, there is not dephasign, the particle diameter that can obtain product by SEM is at 200～600nm, and MWCNTs is evenly distributed between particle.
Li with the MWCNTs modification for preparing 3V 2(PO 4) 3/ C positive electrode (MWCNTs+C=5%) mixes in 91: 6: 3 ratio with adhesive polyvinylidene fluoride (PVDF) and conductive carbon black as electrode active material, add deionized water and stirring and evenly become pasty state, evenly be coated in aluminium foil surface, then with pole piece oven dry 12h under 85 ℃.After the roll squeezer compacting, place vacuum drying oven again electrode slice, divide the positive plate that cuts into lithium ion battery in 90 ℃ of dry 8h.
The electrode slice of making is assembled into lithium ion battery as lithium ion cell positive and battery cathode sheet.Electrolyte is to contain 1mol/L LiPF 6DEC+EC (volume ratio DEC: EC=7: 3), barrier film polypropylene Celgard2300.The battery assembling process is finished in relative humidity is lower than 1% dry glove box.The battery that assembles carries out the constant current charge-discharge test after placing 12h, charging/discharging voltage is 3V～4.3V, circulates under 0.5C～10C charge-discharge magnification (rate of charge is identical with corresponding discharge-rate) in 25 ℃ ± 2 ℃ environment and measures reversible embedding lithium capacity, charge-discharge performance and the high-rate charge-discharge capability of lithium ion cell positive.
The discharge capacity of this routine lithium ion cell positive under different discharge-rates sees Table 1.Cycle performance under different charge-discharge magnifications is seen Fig. 1.
Adopt the Li of MWCNTs modification of the present invention 3V 2(PO 4) 3/ C positive electrode has the performance of following excellence as lithium ion cell positive:
A. charge/discharge capacity height, good cycling stability.The lithium ion cell positive 1C specific discharge capacity of the embodiment of the invention 1, embodiment 2 and embodiment 3 is respectively 128mAh/g, 129mAh/g and 131mAh/g (theoretical specific capacity 133mAh/g), and 100 almost not decay of circulation back capacity.
B. high rate capability excellence.The lithium ion cell positive 5C specific discharge capacity of the embodiment of the invention 1, embodiment 2 and embodiment 3 is respectively 122mAh/g, 123mAh/g and 128mAh/g, the 10C specific discharge capacity is respectively 115mAh/g, 117mAh/g and 122mAh/g, and 150 almost not decay of circulation back capacity.Table 1 is embodiment 1, embodiment 2 and the discharge capacity of embodiment 3 lithium ion cell positives under different discharge-rates.
Table 1
Discharge capacity (mAh/g) 0.5C 1C 5C 10C
Embodiment 1 131 128 122 115
Embodiment 2 131 129 123 117
Embodiment 3 132 131 128 122
C. material conductivity height.The present invention has added the multi-walled carbon nano-tubes (MWCNTs) of high conductivity.Adopt this MWCNTs modification Li 3V 2(PO 4) 3The electronic conductivity of/C composite positive pole is 1.13Scm -1, and Li 3V 2(PO 4) 3The electronic conductivity of/C positive electrode is 4.95 * 10 -3S cm -1, conductivity of electrolyte materials has improved about 200 times after the MWCNTs modification.

Claims (3)

1. the phosphoric acid vanadium lithium composite that is used for lithium ion cell positive is characterized in that it is that amorphous carbon original position by the multi-walled carbon nano-tubes modification coats Li 3V 2(PO 4) 3The powder that the surface forms contains: 95%～98% Li by mass percentage 3V 2(PO 4) 3, 2%～5% carbon.
2. the phosphoric acid vanadium lithium composite material that is used for lithium ion cell positive according to claim 1, the particle diameter that it is characterized in that powder is 200～600nm.
3. prepare the described method that is used for the phosphoric acid vanadium lithium composite material of lithium ion cell positive of claim 1, its step is as follows:
Press Li 3V 2(PO 4) 3Stoichiometric proportion with raw material Li 2CO 3, NH 4H 2PO 4And NH 4VO 3Mix, add the multi-walled carbon nano-tubes and the polyvinyl alcohol that account for raw material gross mass 10～30%, the weight ratio of multi-walled carbon nano-tubes and polyvinyl alcohol is 1: 1, add absolute ethyl alcohol after ball milling on the ball mill mixes, in 850 ℃ of calcining 10h, the amorphous carbon original position that obtains the multi-walled carbon nano-tubes modification coats Li in argon gas atmosphere 3V 2(P0 4) 3The powder that the surface forms.
CN2010102687212A 2010-08-27 2010-08-27 Vanadium-lithium phosphate composite material for positive electrode of lithium ion battery and preparation method thereof Expired - Fee Related CN101937986B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104167548A (en) * 2014-06-04 2014-11-26 上海电力学院 Positive electrode material of lithium ion battery, and preparation method thereof
CN105118994A (en) * 2015-08-26 2015-12-02 武汉理工大学 Positive electrode lithium vanadium phosphate composite material of lithium ion battery and preparation method for positive electrode lithium vanadium phosphate composite material
CN107611431A (en) * 2017-08-22 2018-01-19 天津泰和九思科技有限公司 A kind of lithium vanadium phosphate material and preparation method thereof and lithium ion battery prepared therefrom
CN108539193A (en) * 2018-05-15 2018-09-14 北京科技大学 Include the nucleocapsid NCM tertiary cathode materials and preparation method thereof of carbon nanotube

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101106194A (en) * 2007-07-12 2008-01-16 深圳市贝特瑞电子材料有限公司 Cathode material Li3V2(PO4)3 of lithium ion battery and its making method
CN101186290A (en) * 2007-12-11 2008-05-28 深圳市贝特瑞新能源材料股份有限公司 Anode material vanadium lithium phosphate and preparation method thereof
US20090176159A1 (en) * 2008-01-09 2009-07-09 Aruna Zhamu Mixed nano-filament electrode materials for lithium ion batteries
CN101640263A (en) * 2009-08-27 2010-02-03 杭州海孚新能源科技有限公司 Lithium ion battery composite cathode material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101106194A (en) * 2007-07-12 2008-01-16 深圳市贝特瑞电子材料有限公司 Cathode material Li3V2(PO4)3 of lithium ion battery and its making method
CN101186290A (en) * 2007-12-11 2008-05-28 深圳市贝特瑞新能源材料股份有限公司 Anode material vanadium lithium phosphate and preparation method thereof
US20090176159A1 (en) * 2008-01-09 2009-07-09 Aruna Zhamu Mixed nano-filament electrode materials for lithium ion batteries
CN101640263A (en) * 2009-08-27 2010-02-03 杭州海孚新能源科技有限公司 Lithium ion battery composite cathode material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104167548A (en) * 2014-06-04 2014-11-26 上海电力学院 Positive electrode material of lithium ion battery, and preparation method thereof
CN104167548B (en) * 2014-06-04 2017-02-15 上海电力学院 Positive electrode material of lithium ion battery, and preparation method thereof
CN105118994A (en) * 2015-08-26 2015-12-02 武汉理工大学 Positive electrode lithium vanadium phosphate composite material of lithium ion battery and preparation method for positive electrode lithium vanadium phosphate composite material
CN107611431A (en) * 2017-08-22 2018-01-19 天津泰和九思科技有限公司 A kind of lithium vanadium phosphate material and preparation method thereof and lithium ion battery prepared therefrom
CN108539193A (en) * 2018-05-15 2018-09-14 北京科技大学 Include the nucleocapsid NCM tertiary cathode materials and preparation method thereof of carbon nanotube

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