CN101093888A - Composite material of round LiFePO4 / C in honeycomb structure, and preparation method - Google Patents

Composite material of round LiFePO4 / C in honeycomb structure, and preparation method Download PDF

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Publication number
CN101093888A
CN101093888A CNA2007100725330A CN200710072533A CN101093888A CN 101093888 A CN101093888 A CN 101093888A CN A2007100725330 A CNA2007100725330 A CN A2007100725330A CN 200710072533 A CN200710072533 A CN 200710072533A CN 101093888 A CN101093888 A CN 101093888A
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composite material
lifepo
glucose
preparation
phosphoric acid
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CN100505391C (en
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王殿龙
戴长松
胡信国
李冰
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention solves safety issue existed in anode material of lithium ion battery currently. The issue limits lithium ion battery to be applied to electric automobile. The disclosed product is prepared from NH4FePO4.H2O, Li2CO3 and glucose or cane sugar. Mol ratio between NH4FePO4.H2O and Li2CO3 is 2:1. Mass ratio between C in glucose or cane sugar and LiFePO4 is 1:10-30. NH4FePO4.H2O is prepared from ferrous sulfate, phosphoric acid and ammonia according to mol ratio. Using ultrasonic controlled crystallization process prepares precursor, and using solid state sintering at high temperature prepares composite material. Electrolyte with cellular structure (CS) in the invention can penetrate to inside spherical granules of lithium ferrous phosphate with CS so as to shorten path of solid phase diffusion for lithium ions and to be in favor of charge and discharge in large scaling factor. The anode material is suitable to electric automobile. The method is easy of operation.

Description

The spherical LiFePO of honeycomb 4/ C composite material and preparation method thereof
Technical field
The present invention relates to positive electrode of a kind of power lithium-ion battery and preparation method thereof.
Background technology
Along with people are more and more high to the requirement of living environment quality, also urgent day by day to the demand of electric automobile, countries in the world active development electric vehicle engineering, wherein, the high-power drive pond is one of key technology.Lithium ion battery is because the voltage height, capacity is big, volume is little, in light weight, memory-less effect, special performance such as have extended cycle life, and has broad application prospects and potential great economic benefit in electric automobile market, becomes the focus of research.At present, there is safety issue in anode material for lithium-ion batteries based on cobalt acid lithium, has limited the application of lithium ion battery on electric automobile.Therefore, seek safety and stability more, raw material sources are extensive and cheap, and more the positive electrode of environmental protection is pressing for of development lithium-ion-power cell.LiFePO 4 is as the positive electrode of lithium ion battery of future generation, thermal stability and good cycle, safe, raw material sources extensively, non-environmental-pollution, be the desirable positive electrode of used for electric vehicle power lithium-ion battery.
Summary of the invention
The objective of the invention is in order to solve at present to have limited the problem that lithium ion battery is used on electric automobile, and a kind of honeycomb sphere LiFePO is provided owing to have safety issue based on the anode material for lithium-ion batteries of cobalt acid lithium 4/ C composite material and preparation method thereof.The spherical LiFePO of honeycomb of the present invention 4/ C composite material is a kind of positive electrode of suitable power lithium-ion battery.The present invention adopts ultrasonic wave crystallization control legal system to be equipped with the spherical ferrousphosphate lithium material of honeycomb, and increases electron conduction by the carbon doping, improves the high rate during charging-discharging of power lithium-ion battery.The spherical LiFePO of honeycomb of the present invention 4/ C composite material is by NH 4FePO 4H 2O, Li 2CO 3Make with glucose or sucrose, wherein NH 4FePO 4H 2O and Li 2CO 3Mol ratio be 2: 1, C in glucose or the sucrose and LiFePO 4Mass ratio be 1: 10～30; Described NH 4FePO 4H 2O is made by 1: 1～1.5: 1～1.2 mol ratio by ferrous sulfate, phosphoric acid and ammoniacal liquor.
The spherical LiFePO of honeycomb of the present invention 4The step of/C composite material and preparation method thereof is as follows: one, at 45 ℃, under the ultrasonic stirring condition with frequency 10～30KHz, the phosphoric acid solution of 0.4mol/L and the ammonia spirit of 1.2mol/L are added drop-wise in the copperas solution of 0.6mol/L simultaneously, ferrous sulfate wherein, the mol ratio of phosphoric acid and ammoniacal liquor is 1: 1～1.5: 1～1.2, the rate of addition of phosphoric acid solution is 2/s, the rate of addition of regulating ammoniacal liquor makes the pH value of reactant liquor constant in 2.1, dropwising the back continues to stir 8～12 hours, insulation precipitation again 5～6 hours, then sedimentation and filtration is washed to neutrality again, 110 ℃ of vacuumizes 12 hours, the presoma NH that obtains 4FePO 4H 2O; Two, with presoma NH 4FePO 4H 2O and Li 2CO 3Mixed in 2: 1 in molar ratio, and added glucose or sucrose simultaneously, the addition of glucose or sucrose is C and the LiFePO in glucose or the sucrose 4Mass ratio be 1: 15～30; the deionized water that drips 1%～3% reactant liquor quality grinds, and it is mixed, then at 500～700 ℃ and under the argon shield of hydrogeneous 5～10% (percents by volume); sintering 18 hours, making particle diameter is the spherical LiFePO of 0.1～100 μ m 4/ C composite material.
The spherical LiFePO of honeycomb of the present invention 4The purposes of/C composite material is to be used for lithium ion battery and or to be used for the positive electrode of lithium polymer battery.The spherical LiFePO of honeycomb of the present invention 4/ C composite material has honeycomb, and electrolyte can be penetrated into spherical LiFePO 4 granule interior, has shortened the solid-state diffusion path of lithium ion, helps high power charging-discharging, is suitable for the positive electrode of electric powered motor lithium ion battery; And carbon mixes and has improved the electron conduction of product of the present invention.
Description of drawings
Fig. 1 is the spherical LiFePO of honeycomb 4The microstructure photograph of/C, Fig. 2 is the voltage capacity curve chart of battery constant-current discharge, wherein oral thermometer shows the voltage capacity curve of the 1st cycle battery constant current charge, ■ represents the voltage capacity curve of the 1st cycle battery constant-current discharge, the voltage capacity curve of the 2nd cycle battery constant current charge of zero expression, ● represent the voltage capacity curve of the 2nd cycle battery constant-current discharge, △ represents the voltage capacity curve of the 23rd cycle battery constant current charge, the voltage capacity curve of the 23rd cycle battery constant-current discharge of ▲ expression.
Embodiment
Embodiment one: the spherical LiFePO of honeycomb in the present embodiment 4/ C composite material is by NH 4FePO 4H 2O, Li 2CO 3Make with glucose, wherein NH 4FePO 4H 2O and Li 2CO 3Mol ratio be 2: 1, C in the glucose and LiFePO 4Mass ratio be 1: 10～30; Described NH 4FePO 4H 2O is made by 1: 1～1.5: 1～1.2 mol ratio by ferrous sulfate, phosphoric acid and ammoniacal liquor.
Embodiment two: the mol ratio of present embodiment ferrous sulfate, phosphoric acid and ammoniacal liquor is 1: 1～1.3: 1～1.1.Other is identical with embodiment one.
Embodiment three: the mol ratio of present embodiment ferrous sulfate, phosphoric acid and ammoniacal liquor is 1: 1.2: 1.05.Other is identical with embodiment one.
Embodiment four: that present embodiment adopts is the spherical LiFePO of the synthetic honeycomb of liquid-phase precipitation and high-temperature calcination method 4/ C composite material, detailed process is as follows: one, at 45 ℃, under the ultrasonic stirring condition with frequency 10～30KHz, the phosphoric acid solution of 0.4mol/L and the ammonia spirit of 1.2mol/L are added drop-wise in the copperas solution of 0.6mol/L simultaneously, ferrous sulfate wherein, the mol ratio of phosphoric acid and ammoniacal liquor is 1: 1～1.5: 1～1.2, the rate of addition of phosphoric acid solution is 2/s, the rate of addition of regulating ammoniacal liquor makes the pH value of reactant liquor constant in 2.1, dropwising the back continues to stir 8～12 hours, insulation precipitation again 5～6 hours, then sedimentation and filtration is washed to neutrality again, 110 ℃ of vacuumizes 12 hours, the presoma NH that obtains 4FePO 4H 2O; Two, with presoma NH 4FePO 4H 2O and Li 2CO 3Mixed in 2: 1 in molar ratio, and added glucose simultaneously, the addition of glucose is C and the LiFePO in the glucose 4Mass ratio be 1: 15～30; the deionized water that drips 1%～3% reactant liquor quality grinds, and it is mixed, then at 500～700 ℃ and under the argon shield of hydrogeneous 5～10% (percents by volume); sintering 18 hours, making particle diameter is the spherical LiFePO of 0.1～100 μ m 4/ C composite material.
The LiFePO that (referring to Fig. 1) present embodiment obtains 4/ C composite material has cellular spherical structure.
Embodiment five: the mol ratio of present embodiment ferrous sulfate, phosphoric acid and ammoniacal liquor in step 1 is 1: 1～1.3: 1～1.1.Other is identical with embodiment four.
Embodiment six: the mol ratio of present embodiment ferrous sulfate, phosphoric acid and ammoniacal liquor in step 1 is 1: 1.2: 1.05.Other is identical with embodiment four.
Embodiment seven: present embodiment frequency of ultrasonic in step 1 is 25KHz.Other is identical with embodiment four.
Embodiment eight: the addition of present embodiment glucose in step 2 is C and the LiFePO in the glucose 4Mass ratio be 1: 18～25.Other is identical with embodiment four.
Embodiment nine: the addition of present embodiment glucose in step 2 is C and the LiFePO in the glucose 4Mass ratio be 1: 20.Other is identical with embodiment four.
Embodiment ten: present embodiment reaction temperature in step 2 is 550～650 ℃.Other is identical with embodiment four.
Embodiment 11: present embodiment reaction temperature in step 2 is 550～650 ℃.Other is identical with embodiment four.
Embodiment 12: present embodiment argon gas in step 2 is hydrogeneous to be 6～9% (percents by volume).Other is identical with embodiment four.
Embodiment 13: present embodiment argon gas in step 2 is hydrogeneous to be 8% (percent by volume).Other is identical with embodiment four.
Embodiment 14: the LiFePO that present embodiment makes 4The particle diameter of/C composite material is 10～90 μ m.Other is identical with embodiment four.
Embodiment 15: the LiFePO that present embodiment makes 4The particle diameter of/C composite material is 60 μ m.Other is identical with embodiment four.
Adopt following evidence effect of the present invention, particular content is as follows:
Battery assembling and charge-discharge test: the Experimental cell positive plate is pressed mass ratio LiFePO 4/ C: acetylene black: the mixed of Kynoar=75: 15: 10 is even, adds an amount of NMP and closes cream, is coated in aluminium foil surface then, makes the positive plate that diameter is 14mm, with the positive plate for preparing in 120 ℃ of vacuumize 10h.Adopt the lithium sheet as negative pole, barrier film is Celgard 2400,1molL -1LiFP 6/ EC+DMC (volume ratio is 1: 1) is an electrolyte, is assembled into battery in the argon gas glove box, carries out constant current charge-discharge, and specific discharge capacity is listed in table 1 and Fig. 2.
Table 1
Cycle-index 1 2 23
Specific discharge capacity (mAhg -1) 153 146 144
By above-mentioned result of the test as seen, the spherical LiFePO of honeycomb 4The specific discharge capacity of/C is greater than 140mAhg -1

Claims (10)

1, the spherical LiFePO of a kind of honeycomb 4/ C composite material is characterized in that it is by NH 4FePO 4H 2O, Li 2CO 3Make with glucose or sucrose, wherein NH 4FePO 4H 2O and Li 2CO 3Mol ratio be 2: 1, C in glucose or the sucrose and LiFePO 4Mass ratio be 1: 10～30; Described NH 4FePO 4H 2O is made by 1: 1～1.5: 1～1.2 mol ratio by ferrous sulfate, phosphoric acid and ammoniacal liquor.
2, the spherical LiFePO of honeycomb according to claim 1 4/ C composite material, the mol ratio that it is characterized in that ferrous sulfate, phosphoric acid and ammoniacal liquor is 1: 1～1.3: 1～1.1.
3, the spherical LiFePO of honeycomb according to claim 1 4/ C composite material, the mol ratio that it is characterized in that ferrous sulfate, phosphoric acid and ammoniacal liquor is 1: 1.2: 1.05.
4, the spherical LiFePO of the described honeycomb of a kind of preparation claim 1 4The method of/C composite material, the step that it is characterized in that this method is as follows: one, at 45 ℃, under the ultrasonic stirring condition with frequency 10～30KHz, the phosphoric acid solution of 0.4mol/L and the ammonia spirit of 1.2mol/L are added drop-wise in the copperas solution of 0.6mol/L simultaneously, ferrous sulfate wherein, the mol ratio of phosphoric acid and ammoniacal liquor is 1: 1～1.5: 1～1.2, the rate of addition of phosphoric acid solution is 2/s, the rate of addition of regulating ammoniacal liquor makes the pH value of reactant liquor constant in 2.1, dropwising the back continues to stir 8～12 hours, insulation precipitation again 5～6 hours, then sedimentation and filtration is washed to neutrality again, 110 ℃ of vacuumizes 12 hours, the presoma NH that obtains 4FePO 4H 2O; Two, with presoma NH 4FePO 4H 2O and Li 2CO 3Mixed in 2: 1 in molar ratio, and added glucose or sucrose simultaneously, the addition of glucose or sucrose is C and the LiFePO in glucose or the sucrose 4Mass ratio be 1: 10～30; the deionized water that drips 1%～3% reactant liquor quality grinds, and it is mixed, then at 500～700 ℃ and under hydrogeneous 5～10% argon shield; sintering 18 hours, making particle diameter is the spherical LiFePO of 0.1～100 μ m 4/ C composite material.
5, the spherical LiFePO of honeycomb according to claim 1 4The preparation method of/C composite material is characterized in that frequency of ultrasonic is 25KHz in step 1.
6, the spherical LiFePO of honeycomb according to claim 1 4The preparation method of/C composite material, the addition that it is characterized in that glucose in step 2 are C and the LiFePO in glucose or the sucrose 4Mass ratio be 1: 10～30.
7, the spherical LiFePO of honeycomb according to claim 1 4The preparation method of/C composite material, the addition that it is characterized in that glucose in step 2 are C and the LiFePO in glucose or the sucrose 4Mass ratio be 1: 20.
8, the spherical LiFePO of honeycomb according to claim 1 4The preparation method of/C composite material is characterized in that argon gas hydrogeneous 6%～9% in step 2.
9, the spherical LiFePO of honeycomb according to claim 1 4The preparation method of/C composite material is characterized in that LiFePO 4The particle diameter of/C composite material is 0.1～100 μ m.
10, the spherical LiFePO of honeycomb according to claim 1 4The preparation method of/C composite material is characterized in that LiFePO 4The particle diameter of/C composite material is 60 μ m.
CNB2007100725330A 2007-07-20 2007-07-20 honeycomb structure spherical LiFePO4 / C composite material preparation method Expired - Fee Related CN100505391C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101386405B (en) * 2008-09-28 2010-09-29 江苏双登电源有限公司 Lithium iron phosphate synthetic method
CN102054978A (en) * 2010-11-25 2011-05-11 清华大学 Method for preparing cathode electrode material of nanometer sheet microspheric lithium ion cell
CN102299301A (en) * 2010-06-25 2011-12-28 深圳市比克电池有限公司 Method for reducing electrode polarization of carbon-coated lithium iron phosphate in high current density
CN102393403A (en) * 2011-10-09 2012-03-28 昆明理工大学 Device and method for detecting combustion characteristic of tail gas containing high-concentration CO
CN102479944A (en) * 2010-11-22 2012-05-30 海洋王照明科技股份有限公司 Preparation method and application of lithium iron phosphate composite material
CN103098271A (en) * 2010-09-08 2013-05-08 Sk新技术株式会社 Positive electrode active material for a lithium secondary battery, and method for preparing same
CN103350991A (en) * 2013-05-08 2013-10-16 湖北富邦科技股份有限公司 Ferrous ammonium phosphate sustained-release fertilizer synthesis method
CN108039455A (en) * 2017-12-26 2018-05-15 北京康力优蓝机器人科技有限公司 A kind of preparation method of the positive plate of the lithium rechargeable battery of smart home

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CN103014737A (en) * 2011-09-22 2013-04-03 河南红日锂能源科技有限公司 Cold-rolled steel pickling waste acid treatment method

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101386405B (en) * 2008-09-28 2010-09-29 江苏双登电源有限公司 Lithium iron phosphate synthetic method
CN102299301A (en) * 2010-06-25 2011-12-28 深圳市比克电池有限公司 Method for reducing electrode polarization of carbon-coated lithium iron phosphate in high current density
CN103098271A (en) * 2010-09-08 2013-05-08 Sk新技术株式会社 Positive electrode active material for a lithium secondary battery, and method for preparing same
JP2013541141A (en) * 2010-09-08 2013-11-07 エスケー イノベーション カンパニー リミテッド Anode active material for lithium secondary battery and method for producing the same
CN103098271B (en) * 2010-09-08 2016-03-09 Sk新技术株式会社 For the anode active material and preparation method thereof of lithium secondary battery
US9825294B2 (en) 2010-09-08 2017-11-21 Sk Innovation Co., Ltd. Positive electrode active material for lithium secondary battery and method for preparing the same
CN102479944A (en) * 2010-11-22 2012-05-30 海洋王照明科技股份有限公司 Preparation method and application of lithium iron phosphate composite material
CN102054978A (en) * 2010-11-25 2011-05-11 清华大学 Method for preparing cathode electrode material of nanometer sheet microspheric lithium ion cell
CN102393403A (en) * 2011-10-09 2012-03-28 昆明理工大学 Device and method for detecting combustion characteristic of tail gas containing high-concentration CO
CN103350991A (en) * 2013-05-08 2013-10-16 湖北富邦科技股份有限公司 Ferrous ammonium phosphate sustained-release fertilizer synthesis method
CN103350991B (en) * 2013-05-08 2014-12-31 湖北富邦科技股份有限公司 Ferrous ammonium phosphate sustained-release fertilizer synthesis method
CN108039455A (en) * 2017-12-26 2018-05-15 北京康力优蓝机器人科技有限公司 A kind of preparation method of the positive plate of the lithium rechargeable battery of smart home

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