CN103553064A - Preparation method of lithium ion battery anode material lithium fluoborate - Google Patents

Preparation method of lithium ion battery anode material lithium fluoborate Download PDF

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CN103553064A
CN103553064A CN201310521109.5A CN201310521109A CN103553064A CN 103553064 A CN103553064 A CN 103553064A CN 201310521109 A CN201310521109 A CN 201310521109A CN 103553064 A CN103553064 A CN 103553064A
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lithium
preparation
anode material
boric acid
sintering
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CN103553064B (en
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郑俊超
张宝
明磊
张佳峰
韩亚东
沈超
王健龙
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Central South University
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Central South University
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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
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    • 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 preparation method of a lithium ion battery anode material lithium fluoborate. The preparation method comprises the following steps: (1), mixing a lithium source, an iron source, a boron source and a chelating agent according to the condition that the molar ratio of Li, Fe, B and C is (1-1.05):1:1:(0.5-1.5), adding the mixture into water for dissolving, and controlling the concentration of metal ions at 0.1-0.8mol/L<-1> to obtain liquor; (2), stirring in constant-temperature water bath to form sol; (3), stewing at the constant temperature to form gel; (4), adding water into the gel, and stirring; (5), spraying and drying to obtain a precursor; (6), sintering the precursor for 1.5 hours-2.5 hours at 250 DEG C-350 DEG C in a non-oxidizing atmosphere, then, heating up to 450 DEG C-550 DEG C, sintering for 5 hours-12 hours, and naturally cooling to the room temperature, thereby obtaining LiFeBO3. According to the preparation method disclosed by the invention, material resource is extensive, the operation is simple, convenient and easy to implement, the controllability is strong, the sintering temperature is low and the production cost is low.

Description

A kind of preparation method of anode material for lithium-ion batteries boric acid ferrous lithium
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, relate in particular to a kind of preparation method of anode material for lithium-ion batteries boric acid ferrous lithium.
Background technology
LiFeBO 3it is a kind of Olivine-type Cathode Material in Li-ion Batteries.It has higher specific storage (～220mAh g -1), good electroconductibility (specific conductivity～3.9 * 10 -7s cm -1), minimum volume change (～2%), meanwhile, borate (B0 3) 3-there is less molar mass (58.8), much smaller than similar phosphate radical (P0 4) 3-polyanion (95), and its structure can provide lithium ion conducting and electronic conduction simultaneously, therefore becomes the focus of recent research.Meanwhile, the content of iron in the earth's crust is very high, is only second to oxygen, silicon, aluminium, occupies the 4th, and abundance is 4.75% ，Er China Ye Wei iron resources big country, and the iron resources reserves of wherein having verified account for 9.0% of global total reserves, occupy the 5th, the world; Boron resource is also very abundant in China, and proven reserve account for the 4th, the 16%，Ju world of world's boron rock reserves, so LiFeBO 3it is a kind of anode material for lithium-ion batteries that has very much DEVELOPMENT PROSPECT.
At present, synthetic LiFeBO 3main method be the high-temperature solid phase reaction method under protection of inert gas; and sol-gel method etc.; as CN 102079530 A disclose a kind of method that sol-gel technique is prepared lithium iron borate anode material of lithium ion battery; by ,Peng source, lithium source, source of iron and carbon (1～1.05) in molar ratio: 1:1:2 is soluble in water, controls the concentration of metal ion at 0.1-1molL -1at room temperature stir and within 30 minutes, obtain colloidal sol; then be warmed up to 80 ℃ and keep this temperature 24h; make it to form gel; then after this gel being dried at 120 ℃, ball milling is 2 hours; and then under 20MPa pressure, be pressed into sheet, then under argon shield in 600～900 ℃ of sintering 10 hours, naturally cool to room temperature and obtain LiFeBO 3.The method process is complicated, poor controllability, and sintering temperature is high, and energy consumption is large, is unfavorable for energy-conserving and environment-protective.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of easy to operation, and controllability is strong, and sintering temperature is low, the preparation method of the anode material for lithium-ion batteries boric acid ferrous lithium that energy consumption is low.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of anode material for lithium-ion batteries boric acid ferrous lithium, comprises the following steps:
(1) ratio that is 1-1.05:1:1:0.5-1.5 by lithium source, source of iron, boron source, sequestrant according to the mol ratio of corresponding atom Li, Fe, B, C is mixed, and is added to the water dissolving, controls the concentration of metal ion at 0.1-0.8molL -1, obtaining solution, the concentration of described metal ion is in lithium ion;
(2) step (1) gained solution is placed in to 70-90 ℃ of (preferably 80 ℃) water bath with thermostatic control and stirs the preferred 2h of 1.5-2.5h(), form colloidal sol;
(3) by step (2) gained colloidal sol preferred 0.5h of the standing 0.4-0.6h(of constant temperature under 70-90 ℃ of (preferably 80 ℃) condition), form gel;
(4) in step (3) gained gel, add the moisture of water to lose in replenish step (2) and step (3), stir, make it to form uniform suspension;
(5) step (4) gained suspension is sprayed and be dried, obtain presoma;
(6) step (5) gained presoma is placed in to pipe type sintering furnace, in non-oxidizing atmosphere in 250-350 ℃ of (preferred 280-320 ℃, more preferably 300 ℃) the preferred 2.0h of sintering 1.5-2.5h(), then continue to be warming up to 450-550 ℃ of sintering 5-12h, naturally cool to room temperature, obtain LiFeBO 3.
Further, in step (1), described lithium source is one or more in lithium hydroxide, Quilonum Retard, lithium acetate, lithium oxalate, lithium metaborate, lithium nitrate.
Further, in step (1), described source of iron is one or more in Ferrox, ferrous acetate, ferric oxide, Z 250, iron nitrate, praseodynium iron.
Further, in step (1), described boron source is one or more in boric acid, boron trioxide, tetraboric acid ammonium, lithium metaborate.
Further, in step (1), described sequestrant is one or more in tartrate, citric acid, oxalic acid.
Further, in step (5), spray-drying process inlet temperature is 220 ℃, and temperature out is 130 ℃, and input speed is 1000mLh -1.
Further, in step (6), described non-oxidizing atmosphere is argon gas, nitrogen etc.
The present invention utilizes be dried-Low Temperature Solid-Phase sintering technology of sol-gel-spraying to prepare lithium iron borate anode material of lithium ion battery, raw material sources are extensive, easy to operation, and controllability is strong, sintering temperature is low, can effectively reduce production costs, production process safety and environmental protection, products therefrom is spherical, pattern rule, particle diameter is 0.1-5.0 μ m, and even particle size distribution, is conducive to improve energy density.
accompanying drawing explanation
Fig. 1 is the XRD diffractogram of the embodiment of the present invention 1 gained sample;
Fig. 2 is the SEM figure of the embodiment of the present invention 1 gained sample;
Fig. 3 is the circulation ratio figure of the embodiment of the present invention 1 gained sample.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
0.1mol lithium hydroxide, 0.1mol iron nitrate, 0.025mol tetraboric acid ammonium and 0.013mol citric acid are dissolved in 200mL water, in 80 ℃ of waters bath with thermostatic control, stir 1.5h and obtain colloidal sol, then the standing 0.5h of constant temperature at this temperature, make it to form gel, then add and add water to the former scale of container to supplement the moisture evaporating, after stirring, spraying is dry again obtains presoma, and spray-drying process inlet temperature is 220 ℃, temperature out is 130 ℃, and input speed is 1000mLh -1; Then presoma is placed in to the compacting of magnetic boat, be put in pipe type sintering furnace under nitrogen protection in 300 ℃ of sintering 2h, then continue to be warming up to 500 ℃ of sintering 10h, naturally cool to room temperature, obtain LiFeBO 3.
The XRD diffractogram of the present embodiment gained sample is shown in Fig. 1, and the SEM figure of gained sample is shown in Fig. 2.Using products therefrom as positive electrode material, using metal lithium sheet as negative material, in being full of the glove box of argon gas, be assembled into CR2016 type button cell, in 1.5～4.5V voltage range, carry out charge and discharge cycles, 1/20C first discharge specific capacity is 151.7mAhg -1, the 20 time specific discharge capacity is 127.4mAhg -1, specifically referring to Fig. 3, as from the foregoing, the present embodiment gained sample has excellent cycle performance.
Embodiment 2
0.021mol lithium acetate, 0.02mol praseodynium iron, 0.02mol boric acid, 0.0075mol tartrate are dissolved in 200mL water, in 70 ℃ of waters bath with thermostatic control, stir 2.5h and obtain colloidal sol, then the standing 0.4h of constant temperature at this temperature, make it to form gel, then add and add water to the former scale of container to supplement the moisture evaporating, after stirring, spraying is dry again obtains presoma, and spray-drying process inlet temperature is 220 ℃, temperature out is 130 ℃, and input speed is 1000mLh -1; Then presoma is placed in to the compacting of magnetic boat, be put in pipe type sintering furnace under argon shield in 300 ℃ of sintering 2.5h, then continue to be warming up to 450 ℃ of sintering 12h, naturally cool to room temperature, obtain LiFeBO 3.
Using products therefrom as positive electrode material, using metal lithium sheet as negative material, in being full of the glove box of argon gas, be assembled into CR2016 type button cell, in 1.5～4.5V voltage range, carry out charge and discharge cycles, 1/20C first discharge specific capacity is 164.1mAhg -1, the 20 time specific discharge capacity is 121.2mAhg -1, shown excellent cycle performance.
Embodiment 3
0.0612mol lithium nitrate, 0.06mol Ferrox, 0.03mol boron trioxide, 0.015mol oxalic acid are dissolved in 200mL water, in 80 ℃ of waters bath with thermostatic control, stir 2h and obtain colloidal sol, then the standing 0.5h of constant temperature at this temperature, make it to form gel, then add and add water to the former scale of container to supplement the moisture evaporating, after stirring, spraying is dry again obtains presoma, and spray-drying process inlet temperature is 220 ℃, temperature out is 130 ℃, and input speed is 1000mLh -1; Then presoma is placed in to the compacting of magnetic boat, be put in pipe type sintering furnace under argon shield in 350 ℃ of sintering 2h, then continue to be warming up to 550 ℃ of sintering 5h, naturally cool to room temperature, obtain LiFeBO 3.
Using products therefrom as positive electrode material, using metal lithium sheet as negative material, in being full of the glove box of argon gas, be assembled into CR2016 type button cell, in 1.5～4.5V voltage range, carry out charge and discharge cycles, 1/20C first discharge specific capacity is 179.1mAhg -1, the 20 time specific discharge capacity is 123.2mAhg -1, shown excellent cycle performance.
Embodiment 4
0.078mol Quilonum Retard, 0.15mol ferrous acetate, 0.15mol boric acid and 0.045mol tartrate are dissolved in 200mL water, in 90 ℃ of waters bath with thermostatic control, stir 2.5h and obtain colloidal sol, then the standing 0.5h of constant temperature at this temperature, make it to form gel, then add and add water to the former scale of container to supplement the moisture evaporating, after stirring, spraying is dry again obtains presoma, and spray-drying process inlet temperature is 220 ℃, temperature out is 130 ℃, and input speed is 1000mLh -1; Then presoma is placed in to the compacting of magnetic boat, be put in pipe type sintering furnace under argon shield in 300 ℃ of sintering 2.5h, then continue to be warming up to 550 ℃ of sintering 5h, naturally cool to room temperature, obtain LiFeBO 3.
Using products therefrom as positive electrode material, using metal lithium sheet as negative material, in being full of the glove box of argon gas, be assembled into CR2016 type button cell, in 1.5～4.5V voltage range, carry out charge and discharge cycles, 1/20C first discharge specific capacity is 162.2mAhg -1, the 20 time specific discharge capacity is 134.7mAhg -1, shown excellent cycle performance.
Embodiment 5
0.12mol lithium nitrate, 0.12mol iron nitrate, 0.03mol tetraboric acid ammonium and 0.048mol oxalic acid are dissolved in 200mL water, in 80 ℃ of waters bath with thermostatic control, stir 2h and obtain colloidal sol, then the standing 0.5h of constant temperature at this temperature, make it to form gel, then add and add water to the former scale of container to supplement the moisture evaporating, after stirring, spraying is dry again obtains presoma, and spray-drying process inlet temperature is 220 ℃, temperature out is 130 ℃, and input speed is 1000mLh -1; Then presoma is placed in to the compacting of magnetic boat, be put in pipe type sintering furnace under argon shield in 300 ℃ of sintering 2h, then continue to be warming up to 500 ℃ of sintering 8h, naturally cool to room temperature, obtain LiFeBO 3.
Using products therefrom as positive electrode material, using metal lithium sheet as negative material, in being full of the glove box of argon gas, be assembled into CR2016 type button cell, in 1.5～4.5V voltage range, carry out charge and discharge cycles, 1/20C first discharge specific capacity is 145.2mAhg -1, the 20 time specific discharge capacity is 113.7mAhg -1, shown excellent cycle performance.

Claims (7)

1. a preparation method for anode material for lithium-ion batteries boric acid ferrous lithium, is characterized in that, comprises the following steps:
(1) ratio that is 1-1.05:1:1:0.5-1.5 by lithium source, source of iron, boron source, sequestrant according to the mol ratio of corresponding atom Li, Fe, B, C is mixed, and is added to the water dissolving, controls the concentration of metal ion at 0.1-0.8molL -1, obtaining solution, the concentration of described metal ion is in lithium ion;
(2) step (1) gained solution is placed in to 70-90 ℃ of water bath with thermostatic control and stirs 1.5-2.5h, form colloidal sol;
(3), by step (2) gained colloidal sol standing 0.4-0.6h of constant temperature under 70-90 ℃ of condition, form gel;
(4) in step (3) gained gel, add the moisture of water to lose in replenish step (2) and step (3), stir, make it to form uniform suspension;
(5) step (4) gained suspension is sprayed and be dried, obtain presoma;
(6) step (5) gained presoma is placed in to pipe type sintering furnace, in non-oxidizing atmosphere, in 250-350 ℃ of sintering 1.5-2.5h, then continues to be warming up to 450-550 ℃ of sintering 5-12h, naturally cool to room temperature, obtain LiFeBO 3.
2. the preparation method of anode material for lithium-ion batteries boric acid ferrous lithium according to claim 1, is characterized in that, in step (1), described lithium source is one or more in lithium hydroxide, Quilonum Retard, lithium acetate, lithium oxalate, lithium metaborate, lithium nitrate.
3. the preparation method of anode material for lithium-ion batteries boric acid ferrous lithium according to claim 1 and 2, it is characterized in that, in step (1), described source of iron is one or more in Ferrox, ferrous acetate, ferric oxide, Z 250, iron nitrate, praseodynium iron.
4. the preparation method of anode material for lithium-ion batteries boric acid ferrous lithium according to claim 1 and 2, is characterized in that, in step (1), described boron source is one or more in boric acid, boron trioxide, tetraboric acid ammonium, lithium metaborate.
5. the preparation method of anode material for lithium-ion batteries boric acid ferrous lithium according to claim 1 and 2, is characterized in that, in step (1), described sequestrant is one or more in tartrate, citric acid, oxalic acid.
6. the preparation method of anode material for lithium-ion batteries boric acid ferrous lithium according to claim 1 and 2, is characterized in that, in step (5), spray-drying process inlet temperature is 220 ℃, and temperature out is 130 ℃, and input speed is 1000mLh -1.
7. the preparation method of anode material for lithium-ion batteries boric acid ferrous lithium according to claim 1 and 2, is characterized in that, in step (6), described non-oxidizing atmosphere is argon gas, nitrogen.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140111A (en) * 2014-08-04 2014-11-12 中南大学 Preparation method for nanometer oxide doped with boric acid ferrous lithium cathode materials
CN104821392A (en) * 2015-05-06 2015-08-05 中南大学 Preparation method of spherical lithium ion battery anode material vanadium borate
CN106450238A (en) * 2016-12-08 2017-02-22 湖南博深实业有限公司 Method for preparing lithium ion battery cathode material by coating lithium iron borate with graphene

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102079530A (en) * 2009-11-29 2011-06-01 宁波大学 Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102079530A (en) * 2009-11-29 2011-06-01 宁波大学 Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨驰等: "新型正极材料LiFeBO3的制备和化学性能研究", 《电源技术》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140111A (en) * 2014-08-04 2014-11-12 中南大学 Preparation method for nanometer oxide doped with boric acid ferrous lithium cathode materials
CN104821392A (en) * 2015-05-06 2015-08-05 中南大学 Preparation method of spherical lithium ion battery anode material vanadium borate
CN106450238A (en) * 2016-12-08 2017-02-22 湖南博深实业有限公司 Method for preparing lithium ion battery cathode material by coating lithium iron borate with graphene
CN106450238B (en) * 2016-12-08 2019-07-09 湖南博深实业有限公司 A kind of method that graphene coated iron borate lithium prepares anode material for lithium-ion batteries

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