CN104795563A - Method for manufacturing lithium ion batteries cathode material LiFeBO3/C by citric acid method - Google Patents

Method for manufacturing lithium ion batteries cathode material LiFeBO3/C by citric acid method Download PDF

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Publication number
CN104795563A
CN104795563A CN201410021942.8A CN201410021942A CN104795563A CN 104795563 A CN104795563 A CN 104795563A CN 201410021942 A CN201410021942 A CN 201410021942A CN 104795563 A CN104795563 A CN 104795563A
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lithium
ion batteries
lifebo
citric acid
source
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吴状春
周森森
吴旭敏
李洪阳
陈婷婷
金艳
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Nanjing Connection Micro-Nano Energy Science Co Ltd
Nanjing University of Science and Technology
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Nanjing Connection Micro-Nano Energy Science Co Ltd
Nanjing University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for manufacturing a lithium ion batteries cathode material LiFeBO3/C by a citric acid method. The method comprises the following concrete steps: (1) dissolving a lithium source, an iron source, a fluoroborate source and citric acid in water, and stirring at room temperature for 10 min so as to obtain an aqueous solution; (2) stirring the solution by water bath at 85 DEG C for 4h so as to form gel; (3) drying the gel at 140 DEG C to form a loose and porous solid, taking out the solid and grinding to obtain a powder; and (4) pre-sintering the powder under the protection of Ar gas at 200-250 DEG C for 2h, sintering at 450-650 DEG C for 10h, and carrying out natural cooling to room temperature so as to obtain LiFeBO3/C. The method has the following advantages: sources of raw materials are wide; operation process is simple; production period is short; costs of required equipment are low; calcination temperature is low; and production costs are saved. Particle size of the LiFeBO3/C synthesized by the method is small, granules are uniform, and degree of crystallinity is high. In addition, in-situ carbon-coating is realized by citric acid decomposition. Thus, the lithium ion batteries cathode material has good reversible capacity and good cycle life and can meet actual production application requirements of lithium ion batteries.

Description

A kind of citric acid method prepares anode material for lithium-ion batteries LiFeBO 3the method of/C
Technical field
The present invention relates to a kind of method preparing anode material for lithium-ion batteries, it is specifically related to a kind of citric acid method technology and prepares anode material for lithium-ion batteries LiFeBO 3the method of/C.
Background technology
Lithium ion battery because of its energy density high, open circuit voltage is high, can high power charging-discharging, self discharge is little, environmental friendliness, memory-less effect, the advantages such as cycle life is good are widely used in portable electric appts, electric tool, energy storage device, electric motor car and hybrid electric vehicle.The materials such as now widely used cobalt acid lithium are expensive due to cobalt resource scarcity price, make current lithium battery cost higher.Novel iron system polyanion lithium ion anode material iron borate lithium is due to its theoretical capacity high (220mAh/g), cubical expansivity is little, its similar LiFePO4 quality light (borate is lighter than phosphate radical) relatively, electronic conductance and ionic conductivity high, and China's boron resource and iron resource rich reserves, so exploitation borate family lithium ion anode material has great economic interests and social benefit.
The method of the traditional synthesis iron borate lithium solid reaction process mainly under high temperature inert gas protection; the method complex process; energy consumption is higher; the Homogeneous phase mixing of material is realized by material long-time grinding under organic phase condition; need vacuumize after grinding, the difference of quality of material often causes batch mixing uneven, causes granularity uneven; purity is not high, and chemical property is poor.Legagneur group (Legagneur V, An Y, Mosbah A, et al. LiMBO 3(M=Mn, Fe, Co): synthesis, crystal structure and lithium deinsertion/insertion properties [J]. Solid State Ionics, 2001,139 (1): 37-46.-) the reported first preparation of iron borate lithium anode material and the research of chemical property, material electrochemical performance prepared by electrochemical property test display is poor, Y.Z.Dong(Dong Y Z in 2008, Zhao Y M, Fu P, et al. Phase relations of Li 2o-FeO-B 2o 3ternary system and electrochemical properties of LiFeBO 3compound [J]. Journal of Alloys and Compounds, 2008,461 (1): 585-590.) etc. people to three components Li 2o-FeO-B 2o 3system is studied, and successfully prepare iron borate lithium, but chemical property has much room for improvement.People (the Yamada A such as Yamada in 2010, Iwane N, Harada Y, et al. Lithium Iron Borates as High-Capacity Battery Electrodes [J]. Advanced Materials, 2010,22 (32): 3583-3587.) successfully prepared the iron borate lithium of better performances, but needed the contact of strict discord air, preservation condition is higher.The synthetic technology of these people report is unfavorable for suitability for industrialized production.
The current domestic patent about synthesis iron borate lithium has two.One of them (application number: 201010287627.1) adopt traditional solid reaction process, complex process, energy consumption is high, and grain graininess is large.Another adopt sol-gal process (application number: 200910252885.3) the method and citric acid method similar, but need ball milling in its course of reaction, and sintering temperature is high, energy consumption is large.
Summary of the invention
A kind of citric acid method is the object of the present invention is to provide to prepare anode material for lithium-ion batteries LiFeBO 3the method of/C.The method materials wide material sources, cost is low, is easy to control, and achieves in-situ carbon coated in sintering process, and changes the coated amount of carbon according to different citric acid additions, and the material granule degree obtained is controlled, and carbon covering amount is controlled, excellent electrochemical performance.This method is applicable to industrialization large-scale production.
Realizing technical scheme of the present invention is:
A kind of citric acid method technology of the present invention prepares anode material for lithium-ion batteries LiFeBO 3the method of/C, comprises following implementation step:
(1) by soluble in water to the lithium source of certain stoichiometric proportion, source of iron, boric acid root and citric acid, at room temperature stir and obtain the aqueous solution, then this aqueous solution is stirred at 75 DEG C ~ 95 DEG C temperature, make it to form gel;
(2) this gel is dried at 110 DEG C ~ 150 DEG C, form loose porous solid, take out grind into powder, i.e. iron borate lithium presoma;
(3) by powder in vacuum tube furnace under inert gas shielding in 200 DEG C ~ 250 DEG C pre-burnings, in 450 ~ 650 DEG C of sintering, naturally cool to room temperature, obtain LiFeBO 3/ C.
Wherein, the mol ratio of the lithium source described in step (1), source of iron, boric acid root and citric acid is 1:1:1:1 ~ 3; Described lithium source is one or both in lithium hydroxide, lithium nitrate; Source of iron is ferric nitrate; Boric acid root is boric acid.
Stirred at ambient temperature 10min in step (1), stirs 4h at 75 DEG C ~ 95 DEG C temperature.
In step (1), this aqueous solution stirs under being preferable over 85 DEG C of temperature.
Bake out temperature preferred parameter described in step (2) is 140 DEG C.
Inert gas described in step (3) is one or more in high-purity argon gas, high pure nitrogen, high-purity helium, high-purity neon.
In step (3), sintering process parameter is heating rate is 5 ~ 10 DEG C/min, holding temperature is 200 DEG C ~ 250 DEG C insulation 2 ~ 4h, and during roasting, heating rate is 5 ~ 10 DEG C/min, holding temperature is 450 ~ 650 DEG C of insulation 6 ~ 15h, moves to glove box after then naturally cooling to less than 50 DEG C taking-up grindings.
The present invention, compared with its prior art, has following remarkable advantage feature: (1) adopts citric acid method, reduces sintering temperature, has saved energy consumption in process of production, thus considerably reduced production cost; (2) adopt citric acid method that iron borate lithium presoma can be made to disperse more even, disperse more as well than the ball milling of high temperature solid state reaction, reach molecular level, the material granule size tunable obtained, better crystallinity degree, consistency is high; (3) to can be implemented in building-up process situ carbon coated for citric acid method, adds the conductivity of iron borate lithium, improve its chemical property, make material have higher practical value; (4) this method is simple, and preparation technology, equipment needed thereby are comparatively simple, and the time needed for synthesis is short, and manufacturing cycle is short, and cost is low, is conducive to large-scale industrial production.
  
Accompanying drawing explanation
Fig. 1 is the LiFeBO of gained in the embodiment of the present invention 1 3the XRD figure of/C.
Fig. 2 is the LiFeBO of gained in the embodiment of the present invention 1 3the second time charge and discharge electrograph of/C.
Fig. 3 is the LiFeBO of gained in the embodiment of the present invention 1 3the cycle performance figure of/C.
Fig. 4 is the LiFeBO of gained in the embodiment of the present invention 1 3the SEM figure of/C.
Embodiment
A kind of citric acid method technology of the present invention prepares anode material for lithium-ion batteries LiFeBO 3the method of/C, specifically comprises following implementation step:
Below in conjunction with specific embodiment, the invention will be described further
Example 1
(1) mix: the stoichiometrically lithium source of 1:1:1:1.5, source of iron, boric acid root and citric acid, take lithium hydroxide 2.098g respectively, ferric nitrate 20.200g, boric acid 3.019g, citric acid 15.761g is dissolved in 50ml water, at room temperature stir 10 minutes, make it fully mix, obtain Chinese red clear aqueous solution;
(2) chelatropic reaction: this solution is stirred 4h in the stirred in water bath device of 75 DEG C, makes moisture evaporate to dryness, forms gel;
(3) dry: this gel to be dried at 140 DEG C in vacuum drying chamber, forms loose porous solid, take out grind into powder, i.e. iron borate lithium presoma;
(4) roasting: by powder under Ar gas shielded in vacuum tube furnace in 200 DEG C of pre-burning 2h, in 500 DEG C sintering 10h, naturally cool to room temperature, obtain LiFeBO 3/ C.
Fig. 1 is LiFeBO 3the XRD figure of/C, contrasts PDF card known from figure, and LiFeBO 3peak position is coincide, and is LiFeBO 3phase.
Fig. 2 is LiFeBO 3the second time charge and discharge electrograph of/C, second time recycle ratio capacity can reach 126mAh/g as we know from the figure, and chemical property is good.
Fig. 3 is LiFeBO 3the cycle performance figure of/C, its specific discharge capacity is all upper and lower at 105 mAh/g, and Performance comparision is stablized.
Fig. 4 is LiFeBO 3the SEM figure of/C, as can be seen from the figure granular size reaches micron dimension, and particle is tiny, is evenly distributed.
Example 2
(1) mix: the stoichiometrically lithium source of 1:1:1:3, source of iron, boric acid root and citric acid, take lithium nitrate 3.448g respectively, ferric nitrate 20.200g, boric acid 3.019g, citric acid 31.521g is dissolved in 50ml water, at room temperature stir 10 minutes, make it fully mix, obtain Chinese red clear aqueous solution;
(2) chelatropic reaction: this solution is stirred 4h in the stirred in water bath device of 85 DEG C, makes moisture evaporate to dryness, forms gel;
(3) dry: this gel to be dried at 140 DEG C in vacuum drying chamber, forms loose porous solid, take out grind into powder, i.e. iron borate lithium presoma;
(4) roasting: by powder under Ar gas shielded in vacuum tube furnace in 250 DEG C of pre-burning 2h, in 600 DEG C sintering 10h, naturally cool to room temperature, obtain LiFeBO 3/ C.
  
Example 3
(1) mix: the stoichiometrically lithium source of 1:1:1:1, source of iron, boric acid root and citric acid, take lithium hydroxide 2.098g respectively, ferric nitrate 20.200g, boric acid 3.019g, citric acid 10.507g is dissolved in 50ml water, at room temperature stir 10 minutes, make it fully mix, obtain Chinese red clear aqueous solution;
(2) chelatropic reaction: this solution is stirred 4h in the stirred in water bath device of 95 DEG C, makes moisture evaporate to dryness, forms gel;
(3) dry: this gel to be dried at 140 DEG C in vacuum drying chamber, forms loose porous solid, take out grind into powder, i.e. iron borate lithium presoma;
(4) roasting: by powder under Ar gas shielded in vacuum tube furnace in 250 DEG C of pre-burning 2h, in 600 DEG C sintering 10h, naturally cool to room temperature, obtain LiFeBO 3/ C.
  
Example 4
(1) mix: the stoichiometrically lithium source of 1:1:1:2.5, source of iron, boric acid root and citric acid, take lithium hydroxide 2.098g respectively, ferric nitrate 20.200g, boric acid 3.019g, citric acid 26.268g is dissolved in 50ml water, at room temperature stir 10 minutes, make it fully mix, obtain Chinese red clear aqueous solution;
(2) chelatropic reaction: this solution is stirred 4h in the stirred in water bath device of 85 DEG C, makes moisture evaporate to dryness, forms gel;
(3) dry: this gel to be dried at 140 DEG C in vacuum drying chamber, forms loose porous solid, take out grind into powder, i.e. iron borate lithium presoma;
(4) roasting: by powder under Ar gas shielded in vacuum tube furnace in 250 DEG C of pre-burning 2h, in 600 DEG C sintering 10h, naturally cool to room temperature, obtain LiFeBO 3/ C.
   

Claims (7)

1. a citric acid method prepares anode material for lithium-ion batteries LiFeBO 3the method of/C, is characterized in that concrete implementation step is:
(1) by soluble in water to the lithium source of certain stoichiometric proportion, source of iron, boric acid root and citric acid, at room temperature stir and obtain the aqueous solution, then this aqueous solution is stirred at 75 DEG C ~ 95 DEG C temperature, make it to form gel;
(2) this gel is dried at 110 DEG C ~ 150 DEG C, form loose porous solid, take out grind into powder, i.e. iron borate lithium presoma;
(3) by powder in vacuum tube furnace under inert gas shielding in 200 DEG C ~ 250 DEG C pre-burnings, in 450 ~ 650 DEG C of sintering, naturally cool to room temperature, obtain LiFeBO 3/ C.
2. according to claim 1ly prepare anode material for lithium-ion batteries LiFeBO 3the method of/C, is characterized in that: the mol ratio of the lithium source described in step (1), source of iron, boric acid root and citric acid is 1:1:1:1 ~ 3; Described lithium source is one or both in lithium hydroxide, lithium nitrate; Source of iron is ferric nitrate; Boric acid root is boric acid.
3. according to claim 1ly prepare anode material for lithium-ion batteries LiFeBO 3the method of/C, is characterized in that: stirred at ambient temperature 10min in step (1), stirs 4h at 75 DEG C ~ 95 DEG C temperature.
4. according to claim 3ly prepare anode material for lithium-ion batteries LiFeBO 3the method of/C, is characterized in that: in step (1), this aqueous solution stirs at 85 DEG C of temperature.
5. according to claim 1ly prepare anode material for lithium-ion batteries LiFeBO 3the method of/C, is characterized in that: the bake out temperature parameter described in step (2) is 140 DEG C.
6. according to claim 1ly prepare anode material for lithium-ion batteries LiFeBO 3the method of/C, is characterized in that: the inert gas described in step (3) is one or more in high-purity argon gas, high pure nitrogen, high-purity helium, high-purity neon.
7. according to claim 1ly prepare anode material for lithium-ion batteries LiFeBO 3the method of/C, it is characterized in that: in step (3), sintering process parameter is heating rate is 5 ~ 10 DEG C/min, holding temperature is 200 DEG C ~ 250 DEG C insulation 2 ~ 4h, during roasting, heating rate is 5 ~ 10 DEG C/min, holding temperature is 450 ~ 650 DEG C of insulation 6 ~ 15h, moves to glove box after then naturally cooling to less than 50 DEG C taking-up grindings.
CN201410021942.8A 2014-01-18 2014-01-18 Method for manufacturing lithium ion batteries cathode material LiFeBO3/C by citric acid method Pending CN104795563A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107039643A (en) * 2017-03-27 2017-08-11 上海应用技术大学 A kind of anode material for lithium ion battery and preparation method thereof
CN108134074A (en) * 2017-12-26 2018-06-08 宁波职业技术学院 The preparation method of anode of magnesium ion battery material
CN108751216A (en) * 2018-07-11 2018-11-06 方嘉城 A kind of preparation method of iron borate lithium
CN109659547A (en) * 2018-12-26 2019-04-19 成都其其小数科技有限公司 A kind of binary solid solution borate positive electrode and preparation method for lithium battery
CN109817913A (en) * 2019-01-16 2019-05-28 江西中汽瑞华新能源科技有限公司 A kind of anode material for compound lithium ion battery and preparation method thereof
CN110459737A (en) * 2018-05-07 2019-11-15 福建师范大学 A kind of preparation method and applications of the carbon coating boric acid ferrous iron of core-shell structure

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CN101955190A (en) * 2010-09-20 2011-01-26 四川久远环通电源有限责任公司 Method for preparing lithium iron borate anode material of lithium ion battery
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
JP2011124154A (en) * 2009-12-11 2011-06-23 Panasonic Corp Active material for nonaqueous electrolyte battery, and nonaqueous electrolyte battery
CN102348640A (en) * 2009-03-09 2012-02-08 独立行政法人产业技术综合研究所 Process for producing lithium borate compound

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JP2010092608A (en) * 2008-10-03 2010-04-22 Nec Tokin Corp Cathode for lithium-ion secondary battery and lithium-ion secondary battery using it
CN102348640A (en) * 2009-03-09 2012-02-08 独立行政法人产业技术综合研究所 Process for producing lithium borate compound
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
JP2011124154A (en) * 2009-12-11 2011-06-23 Panasonic Corp Active material for nonaqueous electrolyte battery, and nonaqueous electrolyte battery
CN101955190A (en) * 2010-09-20 2011-01-26 四川久远环通电源有限责任公司 Method for preparing lithium iron borate anode material of lithium ion battery

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107039643A (en) * 2017-03-27 2017-08-11 上海应用技术大学 A kind of anode material for lithium ion battery and preparation method thereof
CN107039643B (en) * 2017-03-27 2019-05-24 上海应用技术大学 A kind of anode material for lithium ion battery and preparation method thereof
CN108134074A (en) * 2017-12-26 2018-06-08 宁波职业技术学院 The preparation method of anode of magnesium ion battery material
CN110459737A (en) * 2018-05-07 2019-11-15 福建师范大学 A kind of preparation method and applications of the carbon coating boric acid ferrous iron of core-shell structure
CN110459737B (en) * 2018-05-07 2022-03-18 福建师范大学 Preparation method and application of carbon-coated ferrous borate with core-shell structure
CN108751216A (en) * 2018-07-11 2018-11-06 方嘉城 A kind of preparation method of iron borate lithium
CN108751216B (en) * 2018-07-11 2019-11-22 方嘉城 A kind of preparation method of iron borate lithium
CN109659547A (en) * 2018-12-26 2019-04-19 成都其其小数科技有限公司 A kind of binary solid solution borate positive electrode and preparation method for lithium battery
CN109817913A (en) * 2019-01-16 2019-05-28 江西中汽瑞华新能源科技有限公司 A kind of anode material for compound lithium ion battery and preparation method thereof

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