CN1792780A - Zinc ion mixed olivine structure LiFePo4 and its preparation process and application - Google Patents

Zinc ion mixed olivine structure LiFePo4 and its preparation process and application Download PDF

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Publication number
CN1792780A
CN1792780A CNA2005100307773A CN200510030777A CN1792780A CN 1792780 A CN1792780 A CN 1792780A CN A2005100307773 A CNA2005100307773 A CN A2005100307773A CN 200510030777 A CN200510030777 A CN 200510030777A CN 1792780 A CN1792780 A CN 1792780A
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lifepo
lithium
salt
zine ion
olivine structural
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CN100340475C (en
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刘浩
李晨
吴宇平
吴浩青
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Fudan 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
    • 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

A Zn ion doped LiFePO4 with olivinite structure used for preparing the positive electrode of Li ion battery is prepared through doping the Zn ions into the LiFePO4 by solid-phase method or sol-gel method.

Description

The adulterated olivine structural LiFePO of a kind of zine ion 4And its production and use
Technical field
The invention belongs to the electrochemical material technical field, be specifically related to a kind of LiFeP that mixes the olivine structural of zinc O4 and its production and use.
Background technology
As everyone knows, LiFePO 4 (LiFePO 4) having caused more and more insiders' concern as promising cell positive material, major cause is the LiFePO of olivine structural 4Material has higher current potential, and the high theoretical capacity is nontoxic to environment, and excellent cycle performance is arranged, and thermostability is considered to LiCoO 2Substitute.But because LiFePO 4Electronic conductance is lower, and capacity attenuation is fast during high current charge-discharge, makes material that big problem be arranged in application.At present mainly by coated with carbon (see civilian Journal of Power Sources for details, 2001,97-98 rolls up the 503rd page the-the 507th page; Journal of Electrochemical Society, 2002,149 volume A1184 page or leaf-Di A1189 pages or leaves), adding nanometre metal powder (as Au, Cu etc., sees civilian Electrochemical and Solid StateLetters for details, 50 pages of 2002,5 volume A47 page or leaf-Di; Solid State Communications, 2004,129 volumes, the 311st page the-the 314th page) or cation doping (Mg for example 2+, Al 3+, Ti 4+, Zr 4+, Nb 6+Or W 6+, see civilian Nature Materials for details, 2002, the 1 the volume the 123rd page the-the 128th page) method improve specific conductivity.
Although aforesaid method can improve electric conductivity, can not obviously improve LiFePO 4The embedding lithium and take off the embedding reversibility, when practical application, have obvious voltage delay phenomenon.Be necessary to be further improved.
Summary of the invention
The objective of the invention is to propose the LiFePO of the high olivine structural of a kind of electric conductivity 4Material and its production and use.
The LiFePO of the olivine structural that the present invention proposes 4(LiFePO 4) is the LiFePO of the adulterated olivine structural of a kind of zine ion 4, the particle diameter of its one-level particle is less than 800nm.This material structure is stable, even particle distribution, and embedding lithium and take off the embedding good reversibility, chemical property is good; Can be used as anode material for lithium-ion batteries, be assembled into lithium ion battery.
The present invention also proposes the LiFePO of zine ion doping olivine structural 4The preparation method, concrete steps are as follows:
(1) introducing of zine ion: with raw material lithium salts, phosphoric acid salt, ferrous salt with contain the zine ion compound and mix, and mix, adopt solid phase ball milling or sol-gel method to make raw material evenly mixed, wherein mole proportioning Li: Zn: Fe: PO with carbon source by the mole proportioning 4=1: 0.001-0.10: 0.999-0.90: 0.9-1.1, in the synthetic materials, the content of carbon is 10ppm-50%;
(2) decomposition reaction: with step (1) products therefrom under the protection of rare gas element or reducing gas in 200～400 ℃ of heating 1 minute～60 hours, raw material is decomposed;
(3) grind: step (2) gained mixture is ground, to being evenly distributed;
(4) high-temperature calcination: the product of step (3) gained was calcined 1～40 hour down in 500～900 ℃ under rare gas element or reducing gas protection.
In above-mentioned preparation method of the present invention, the raw material that step (1) relates to, wherein, lithium salts is that Quilonum Retard, lithium hydroxide, lithium nitrate or other heat labile lithium salts (comprising organic lithium salt), phosphoric acid salt can be ammonium hydrogen phosphate (comprising primary ammonium phosphate, Secondary ammonium phosphate) or ammonium phosphate etc., ferrous salt can be Ferrox or iron protoxide, also can be other labile ferrous salt (comprising organic ferrous salt); Containing the zine ion compound can be zinc oxide, also can be zinc hydroxide or other labile zinc salt; Carbon source can adopt simple substance carbon (as carbon black, graphite etc.), also can adopt carbohydrate (as sucrose, glucose etc.) or other all carbonaceous organic materials (as citric acid, tartrate etc.), carbon in the synthetic materials (C) mass content is 10ppm-50%, preferred 1%-20%.Rotational speed of ball-mill influences the degree that mixes of raw material in the solid phase ball milled, and rotating speed adopts 100～3600 rev/mins, and preferred 100～500 rev/mins, most preferably 350～400 rev/mins.The ball milling time is chosen 1～48 hour, preferred 15～25 hours.
Step (2) relates to the preliminary decomposition of step (1) gained blended stock.Decomposition temperature depends on raw-material structure, can determine preferred temperature by the thermal weight loss experiment.With the solid phase ball milled is example, and adopting temperature is 200～400 ℃, and more preferably 250～350 ℃, optimum is 300 ℃.Resolving time adopted 1 minute～60 hours, and preferred 5～20 hours, most preferably 10～12 hours.For avoiding ferrous ion when heating oxidized, take inert atmosphere or protection of reducing atmosphere, pre-ventilation 1 minute～10 hours is with excluding air before the heating.The dispersion agent effect is played in the adding of carbon source on the one hand, prevents the LiFePO 4 particle agglomeration; Protect ferrous ion oxidized on the other hand.
Step (3) relates to the uniform mixing that step (2) is decomposed back gained mixture, is beneficial to next step high-temperature calcination and forms and stablize the crystal formation material.
Step (4) relates to the high-temperature calcination of the mixture of step (3) gained.This step more preferably 600～800 ℃, is carried out in tube furnace under optimum 700～750 ℃ the temperature preferably at 500～900 ℃.Calcining temperature is bigger to the material property influence: temperature is crossed the low ferric iron dephasign that exists; The too high particle of temperature is easily grown up, and influences utilising efficiency.Calcination atmosphere is inert atmosphere (for example Ar, Ne, He, Xe, N 2) or reducing gas (H for example 2/ Ar gas mixture) reacts under the condition.Calcination time can be 1～40 hour, preferred 5～20 hours, and most preferably 10～15 hours.
The present invention's used wording " zine ion doping " in term " LiFePO 4 of zine ion doping olivine structural " is meant in solid phase method of the present invention or Prepared by Sol Gel Method process, make zine ion enter the LiFePO 4 lattice through mixing and high-temperature calcination, form the compound of stable uniform.The doping of zine ion increases the unit cell parameters in the LiFePO 4 lattice, thereby can make lithium ion take off embedding and the reversibility when embedding is improved the minimizing voltage delay.
The contriver thinks among the present invention that the reactant degree that mixes has a significant impact the synthetic material property in the building-up process, so the solid phase ball milled must adopt rotational speed of ball-mill faster and long ball milling time to guarantee the thorough mixing of raw material.The carbon source that evenly makes of material is uniformly distributed in blended stock, and particle is not reunited when guaranteeing high-temperature calcination, more can not produce caking phenomenon, thereby effectively control the particulate growth.
The olivine structural that the adulterated LiFePO 4 of zine ion that is prepared by the present invention has standard, being doped with of zine ion is beneficial to the increase unit cell parameters, improves the reversibility that lithium ion takes off embedding and embedding; Even particle size is disperseed better in addition.At last, the inventive method is workable, favorable reproducibility, and the prepared constant product quality that gets.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the embodiment of the invention 2 gained zine ion doping olivine structural LiFePO 4s.
Fig. 2 is the cycle performance figure of Comparative Examples of the present invention and embodiment gained zine ion doping olivine structural LiFePO 4.
Embodiment
Be described in more detail below by reference Comparative Examples and embodiment, but protection scope of the present invention is not limited to these embodiment.
Comparative Examples
With raw material lithium salts, phosphoric acid salt, ferrous salt Li: Fe: PO in molar ratio 4=1: mix at 1: 1, and mix with 5% acetylene black, with 400 rev/mins rotating speed ball millings 24 hours, the blended stock that obtains mixing.300 ℃ of heating made raw material decompose in 12 hours in protection of inert gas pipe type stove then.Obtain the black powder product after the decomposition, after the grinding evenly, place tube furnace once more, under inert atmosphere protection, calcined 15 hours for 750 ℃, obtain the LiFePO 4 of undoped olivine structural, molecular formula LiFePO 4The synthetic material records unit cell parameters through X-ray powder diffraction: a=5.9899 , b=10.2841 , c=4.7299 , unit cell volume V=291.4 3With proportioning LiFePO 4: adhesive PVDF: acetylene black=90: 5: 5 mixes and obtains active substances in cathode materials, is negative pole with the lithium sheet, and LB315 is an electrolytic solution, and Celgard2400 is a barrier film, is assembled into the model battery in glove box.Cyclic voltammetry curve records redox peak separation 0.97V by CHI400 electrochemical workstation determination of scan rate with 0.1mV/s in 2.2 to 4.5 volt range.The cycle performance test is at room temperature measured in 2.7 to 4.0 volt range by the LAND battery test system, and loading capacity is 122mAh/g first, and 10 times the circulation back is 74mAh/g.
Embodiment 1
With raw material lithium salts, phosphoric acid salt, ferrous salt and zinc compound Li: Zn: Fe: PO in molar ratio 4=1: mix at 0.01: 0.99: 1, and mix with 5% carbon source material, with 400 rev/mins rotating speed ball millings 24 hours, the blended stock that obtains mixing.Under protection of inert gas, 300 ℃ were heated 10 hours in tube furnace then, and raw material is decomposed.The decomposition after product is a black powder, places tube furnace once more after grinding evenly, and 750 ℃ of calcinings are 15 hours under protection of inert gas, the LiFePO 4 of the olivine structural of the zine ion 1% that obtains mixing, molecular formula LiZn 0.01Fe 0.99PO 4The same Comparative Examples of unit cell parameters calculating, cyclic voltammetry and volume test, the material unit cell parameters is: a=6.0014 , b=10.3206 , c=4.7394 , unit cell volume V=293.7 3Record redox peak separation 0.40V; Loading capacity is 148mAh/g first, and 10 times the circulation back is 131mAh/g.
Embodiment 2
With raw material lithium salts, phosphoric acid salt, ferrous salt and zinc compound Li in molar ratio: zine ion: Fe: PO 4=1: mix at 0.02: 0.98: 1, and mix with 5% acetylene black, with 400 rev/mins rotating speed ball millings 24 hours, the blended stock that obtains mixing.300 ℃ of heating made raw material decompose in 12 hours in protection of inert gas pipe type stove then.The decomposition after product is a black powder, places tube furnace once more after the grinding evenly, at reducing atmosphere (H 2/ Ar volume ratio=0.05/1) the following 700 ℃ of calcinings of protection are 24 hours, and obtaining molecular formula is LiZn 0.02Fe 0.98PO 4The ferrousphosphate lithium material of olivine structural of doping zine ion 2%.The same Comparative Examples of unit cell parameters calculating, cyclic voltammetry and volume test, the material unit cell parameters is: a=6.0043 , b=10.3250 , c=4.7041 , unit cell volume V=291.6 3CV records redox peak separation 0.33V; Loading capacity is 140mAh/g first, and 10 times the circulation back is 120mAh/g.
Embodiment 3
With raw material lithium salts, phosphoric acid salt, ferrous salt and zinc compound Li: Zn: Fe: PO in molar ratio 4=1: mix at 0.05: 0.95: 1, and mix with 5% acetylene black, with 400 rev/mins rotating speed ball millings 24 hours, the blended stock that obtains mixing.300 ℃ of heating made raw material decompose in 12 hours in protection of inert gas pipe type stove then.The decomposition after product is a black powder, places tube furnace once more after the grinding evenly, at reducing atmosphere (H 2/ Ar volume ratio=0.05/1) the following 750 ℃ of calcinings of protection are 15 hours, the LiFePO 4 of the olivine structural of the zine ion 5% that obtains mixing, molecular formula LiZn 0.05Fe 0.95PO 4The same Comparative Examples of unit cell parameters calculating, cyclic voltammetry and volume test, the material unit cell parameters is: a=6.1071 , b=10.3762 , c=4.7403 , V=300.49 3Record redox peak separation 0.51V by CV; Loading capacity is 138mAh/g first, and 10 times the circulation back is 148mAh/g.
Embodiment 4
With raw material Iron nitrate, zinc nitrate and lithium acetate Li: Zn: Fe: PO in molar ratio 4=1: mix at 0.08: 0.92: 1, be dissolved in the nitric acid of 1M, dropwise be added drop-wise to then in the citric acid solution, ceaselessly stir in the dropping process, add the saturated solution of phosphoric acid ammonium dihydrogen at last in this mixed solution.The gel that forms is dried, is dewatered under 60 ℃ in retort furnace, presoma grinds the back and decompose 5h in the inert atmosphere under 300 ℃ in tube furnace, behind the regrinding in tube furnace argon gas atmosphere, 600 ℃ calcining 10h down, obtain mixing zine ion 8% the LiFePO 4 of olivine structural, molecular formula LiZn 0.08Fe 0.92PO 4The same Comparative Examples of unit cell parameters calculating, cyclic voltammetry and volume test, the material unit cell parameters is: a=6.0970 , b=10.3550 , c=4.7398 , unit cell volume V=299.2 3Record redox peak separation 0.38V by CV.Loading capacity is 141.7mAh/g first, and 10 times the circulation back is 136mAh/g.
Embodiment 5
With raw material lithium salts, phosphoric acid salt, ferrous salt and zinc compound according to mol ratio Li: Zn: Fe: PO 4=1: mix at 0.10: 0.90: 1, and mix with 5% acetylene black, with 400 rev/mins rotating speed ball millings 24 hours, the blended stock that obtains mixing.300 ℃ of heating made raw material decompose in 12 hours in protection of inert gas pipe type stove then.The decomposition after product is a black powder, places tube furnace once more after the grinding evenly, at reducing atmosphere (0.05H 2/ Ar) following 750 ℃ of calcinings of protection 15 hours, the LiFePO 4 of the olivine structural of the zine ion 10% that obtains mixing, molecular formula LiZn 0.1Fe 0.9PO 4Unit cell parameters is calculated and the same Comparative Examples of cyclic voltammetry, and the material unit cell parameters is: a=5.9970 , b=10.3250 , c=4.7368 , unit cell volume V=293.3 3Record redox peak separation 0.31V by CV.Loading capacity is 135mAh/g first, and 10 times the circulation back is 129mAh/g.
Result by above embodiment compares with Comparative Examples, can find out obviously that the present invention prepares unit cell volume than Comparative Examples certain increase is arranged, it is slotting to help taking off of lithium ion more; The peak-to-peak spacing of each embodiment redox all reduces to some extent than Comparative Examples, has shown the reversible raising of system, the embedding of lithium ion and deviate from rapider; The doping of more also showing of cycle performance: Zn has improved the cycle performance of material in addition, and capacity attenuation is slower.

Claims (7)

1, a kind of adulterated olivine structural LiFePO 4Material is characterized in that the LiFePO for the adulterated olivine structural of zine ion 4, the particle diameter of its one-level particle is less than 800nm.
2, a kind of doping olivine structural LiFePO as claimed in claim 1 4Preparation methods is characterized in that concrete steps are as follows:
(1) introducing of zine ion: with raw material lithium salts, phosphoric acid salt, ferrous salt with contain the zine ion compound and mix, and mix, adopt solid phase ball milling or sol-gel method to make raw material evenly mixed, wherein mol ratio Li: Zn: Fe: PO with carbon source by the mole proportioning 4=1: 0.001-0.10: 0.999-0.90: 0.9-1.1, in the synthetic materials, the content of carbon is 10ppm-50%;
(2) decomposition reaction: with step (1) products therefrom under the protection of rare gas element or reducing gas in 200～400 ℃ of heating 1 minute～60 hours, raw material is decomposed;
(3) grind: step (2) gained mixture is ground, to being evenly distributed;
(4) high-temperature calcination: the product of step (3) gained was calcined 1～40 hour down in 500～900 ℃ under rare gas element or reducing gas protection.
3, preparation method according to claim 1 is characterized in that, said lithium salts is Quilonum Retard, lithium nitrate or lithium hydroxide, and perhaps other heats labile inorganic or organic lithium salt; Said phosphoric acid salt is ammonium hydrogen phosphate or ammonium phosphate; Said ferrous salt is that iron protoxide or other heat labile inorganic or organic ferrous salt.
4, preparation method according to claim 1 is characterized in that the said zine ion compound that contains is a zinc oxide, and zinc hydroxide or other heat labile inorganic or organic zinc salt.
5, preparation method according to claim 1 is characterized in that said carbon source is selected from carbohydrate or carbonaceous organic material.
6, preparation method according to claim 1 is characterized in that 100～3600 rev/mins of the middle rotational speed of ball-mill of step (1), and the ball milling time is chosen 1～48 hour.
7, a kind of adulterated olivine structural LiFePO as claimed in claim 1 4Material is as the application of anode material for lithium-ion batteries.
CNB2005100307773A 2005-10-27 2005-10-27 Zinc ion mixed olivine structure LiFePo4 and its preparation process and application Expired - Fee Related CN100340475C (en)

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CN101814601A (en) * 2010-03-11 2010-08-25 彩虹集团公司 Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate
CN102306753A (en) * 2011-09-03 2012-01-04 深圳市贝特瑞新能源材料股份有限公司 Full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate
CN102324494A (en) * 2010-07-20 2012-01-18 上海大象能源科技有限公司 Lithium iron phosphate / nano-powder tube oxide composite cathode material and preparation method thereof
CN105449206A (en) * 2015-12-23 2016-03-30 邬石根 LiFe1-xZrxPO4 electrode material and preparation method thereof
CN105514428A (en) * 2015-12-23 2016-04-20 邬石根 Composite electrode material and preparation technology thereof
EP2562858A4 (en) * 2010-04-21 2017-01-25 LG Chem, Ltd. Carbon-coated lithium iron phosphate with olivine crystal structure and lithium secondary battery using the same
CN107126951A (en) * 2017-03-27 2017-09-05 浙江师范大学 A kind of preparation method of zinc doping tungstic acid
CN107265431A (en) * 2017-05-22 2017-10-20 昆明理工大学 A kind of method for preparing phosphate of olivine type positive electrode
WO2023116019A1 (en) * 2021-12-22 2023-06-29 广东邦普循环科技有限公司 Lithium iron phosphate material and preparation method therefor

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CN101814601B (en) * 2010-03-11 2012-07-04 彩虹集团公司 Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate
CN101814601A (en) * 2010-03-11 2010-08-25 彩虹集团公司 Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate
EP2562858A4 (en) * 2010-04-21 2017-01-25 LG Chem, Ltd. Carbon-coated lithium iron phosphate with olivine crystal structure and lithium secondary battery using the same
US9812707B2 (en) 2010-04-21 2017-11-07 Lg Chem, Ltd. Carbon-coated lithium iron phosphate of olivine crystal structure and lithium secondary battery using the same
CN102324494A (en) * 2010-07-20 2012-01-18 上海大象能源科技有限公司 Lithium iron phosphate / nano-powder tube oxide composite cathode material and preparation method thereof
CN102324494B (en) * 2010-07-20 2014-10-01 甘肃大象能源科技有限公司 Lithium iron phosphate / nano-powder tube oxide composite cathode material and preparation method thereof
CN102306753B (en) * 2011-09-03 2013-12-18 深圳市贝特瑞新能源材料股份有限公司 Full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate
CN102306753A (en) * 2011-09-03 2012-01-04 深圳市贝特瑞新能源材料股份有限公司 Full solid phase preparation method of lithium ion positive electrode material lithium iron phosphate
CN105514428A (en) * 2015-12-23 2016-04-20 邬石根 Composite electrode material and preparation technology thereof
CN105449206A (en) * 2015-12-23 2016-03-30 邬石根 LiFe1-xZrxPO4 electrode material and preparation method thereof
CN107126951A (en) * 2017-03-27 2017-09-05 浙江师范大学 A kind of preparation method of zinc doping tungstic acid
CN107126951B (en) * 2017-03-27 2020-04-17 浙江师范大学 Preparation method of zinc-doped tungsten trioxide
CN107265431A (en) * 2017-05-22 2017-10-20 昆明理工大学 A kind of method for preparing phosphate of olivine type positive electrode
CN107265431B (en) * 2017-05-22 2021-06-18 昆明理工大学 Method for preparing olivine type phosphate anode material
WO2023116019A1 (en) * 2021-12-22 2023-06-29 广东邦普循环科技有限公司 Lithium iron phosphate material and preparation method therefor
GB2616238A (en) * 2021-12-22 2023-08-30 Guangdong Brunp Recycling Technology Co Ltd Lithium iron phosphate material and preparation method therefor

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