CN102751498A - Preparation method of anode material ferric pyrophosphate lithium of lithium ion battery - Google Patents

Preparation method of anode material ferric pyrophosphate lithium of lithium ion battery Download PDF

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CN102751498A
CN102751498A CN2012102551974A CN201210255197A CN102751498A CN 102751498 A CN102751498 A CN 102751498A CN 2012102551974 A CN2012102551974 A CN 2012102551974A CN 201210255197 A CN201210255197 A CN 201210255197A CN 102751498 A CN102751498 A CN 102751498A
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lithium
iron
source
fep
preparation
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CN102751498B (en
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余志勇
刘韩星
钱俊
姚兰
郝华
曹明贺
尧中华
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Wuhan University of Technology WUT
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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 preparation method of anode material ferric pyrophosphate lithium of a lithium ion battery and belongs to the field of a new energy source material. The preparation method comprises the processes: mixing a lithium source, an iron source and a phosphorus source according to the ratio that the molar ratio of Li to Fe to P2 is 2 to 1 to 2; uniformly mixing the materials by ball-milling, then drying, grinding, tableting and transferring the materials to a calcining furnace, pre-sintering the material under protective atmosphere, wherein the pre-sintering temperature is 200-400 DEG C, the pre-sintering time is 5-15 hours, and the heating rate is 1-5 DEG C per minute; grinding and tableting the obtained pre-sintered material, and then calcining the material at high temperature, wherein the calcining temperature is 600-800 DEG C, the calcining time is 3-24 hours, and the heating rate is 1-5 DEG C per minute; then taking out the calcined material, and grinding the material to obtain the Li2Fe2P2O7 (ferric pyrophosphate lithium) anode material. The preparation method has the characteristics that the material source is wide, the price is low, the process is simple, and the industrial large-scale production is easily implemented.

Description

A kind of preparation method of anode material for lithium-ion batteries ferric pyrophosphate lithium
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries ferric pyrophosphate lithium, belong to the new energy materials field.
Background technology
Chemical power source (battery) is a kind of device that chemical energy is changed into electric energy through chemical reaction; Be that the energy stores and one of important way that transforms; In industrial, military and human daily life, having obtained using widely, is the important tool of alleviating current energy crisis and reducing environmental pollution.
In secondary cell, lithium ion battery because have the operating voltage height, have extended cycle life, capacity is big, volume is little, self discharge is little, advantages such as few are polluted in memory-less effect and environmental protection, becomes the first-selection in the chargeable source of current portable type electronic product rapidly.For lithium ion battery, positive electrode has conclusive effect to its capacity, and closely bound up with battery cost, security performance, and oneself becomes the key factor that restriction lithium ion battery overall performance further improves positive electrode.Therefore, the exploitation of new type lithium ion battery positive electrode seems particularly important.
The Shin-ichi Nishimura of Tokyo Univ Japan in 2010 is at New Lithium Iron Pyrophosphate as 3.5 V Class Cathode Material for Lithium Ion Battery (J. A M. CHEM. SOC. 2010; 132; 13596 – 13597) report adopts the divalence source of iron in, has synthesized a kind of anode material for lithium-ion batteries Li of novel phosphate system 2FeP 2O 7This material has the voltage platform about 3.5V, and theoretical capacity is high, good cycle.Because the divalence source of iron costs an arm and a leg, and be difficult to preserve, this patent uses cheap ferric iron source, adopts a kind of new method to synthesize Li 2FeP 2O 7Material.
Summary of the invention
The object of the present invention is to provide a kind of anode material for lithium-ion batteries Li 2FeP 2O 7The preparation method, the Li that makes with this method 2FeP 2O 7Positive electrode purity is high, and the electrochemistry capacitance of material is high, good cycle.
The objective of the invention is to realize through following technical scheme.
A kind of anode material for lithium-ion batteries Li 2FeP 2O 7The preparation method, comprise following process:
1) with lithium source, inorganic source of iron, organic source of iron and phosphorus source, carry out weighing according to proportioning, use the ethanol mixing and ball milling then, the slurry that mixes is prepared calcining behind the compound process grinding that obtains, the compressing tablet after drying is removed ethanol;
2) the compressing tablet material that step 1) is obtained is put into calciner, pre-burning under protective atmosphere, and calcined temperature is 200～400 ℃; 5～15 hours pre-burning time, intensification degree rate is 1～5 ℃/min, at high temperature calcines behind the grinding of gained pre-burning material, the compressing tablet; Calcining heat is 600～800 ℃, and calcination time is 3～24 hours, and intensification degree rate is 1～5 ℃/min; Take out the calcining material then, obtain Li after the grinding 2FeP 2O 7Positive electrode;
Wherein proportioning raw materials is that the Li:Fe:P mol ratio is 2:1:2, and the consumption of organic source of iron is according to its contained organic acid and the theoretical Li that generates 2FeP 2O 7The mass ratio of required organic acid is 10%～40% to take by weighing, and iron in shortage is supplied with inorganic source of iron.
Above-mentioned steps 1) the lithium source described in is lithium carbonate, lithium hydroxide, lithium oxalate or lithium acetate.
Above-mentioned steps 1) the inorganic source of iron described in is iron oxide, tri-iron tetroxide or iron hydroxide.
Above-mentioned steps 1) the organic source of iron described in is ironic citrate, ferric oxalate or ferric acetate.
Above-mentioned steps 1) the phosphorus source described in is diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.
Above-mentioned steps 2) protective atmosphere described in is the mist of nitrogen, argon gas or hydrogen and argon gas.
Compared with prior art, the present invention has the following advantages: synthesis of anode material of lithium-ion battery Li 2FeP 2O 7Technology simple, be prone to realize industrial-scale production; The raw material wide material sources, cheap.
Description of drawings
Fig. 1 is to be example Li with embodiment 1 gained sample 2FeP 2O 7The XRD figure picture
Fig. 2 is to be example Li with embodiment 1 gained sample 2FeP 2O 7SEM image (amplifying 5000 times)
Fig. 3 is to be example Li with embodiment 1 gained sample 2FeP 2O 7SEM image (amplifying 20000 times)
Fig. 4 is to be example gained first charge-discharge curve with embodiment 1 gained sample.
Embodiment
Through specific embodiment the present invention is done detailed description below, following embodiment only is used to explain the present invention, but and is not used in and limits practical range of the present invention.
Embodiment 1:
To analyze pure lithium carbonate, ammonium dihydrogen phosphate and ironic citrate is lithium source, phosphorus source and source of iron.According to the Li:Fe:P mol ratio is the ratio weighing raw materials of 2:1:2, and the consumption of organic source of iron ironic citrate is according to citrate and the theoretical Li that generates 2FeP 2O 7Mass ratio 10% take by weighing, iron in shortage is supplied with inorganic source of iron tri-iron tetroxide.Reaction raw materials is placed ball grinder, add slurry drying under 100 ℃ that ethanol obtains behind ball mill mixing.Dried compound grind and compressing tablet after under argon shield, rise to 200 ℃ and carry out predecomposition and handle 15h with the speed of 1 ℃/min; Material after predecomposition is handled grinds evenly and compressing tablet; Under the atmosphere identical with the predecomposition processing, rise to 600 ℃ of calcining 24h with the phase same rate then, cooling, grinding back products therefrom are Li 2FeP 2O 7Material.
Embodiment 2:
To analyze pure lithium oxalate, diammonium hydrogen phosphate and ferric oxalate is lithium source, phosphorus source and source of iron.According to the Li:Fe:P mol ratio is the ratio weighing raw materials of 2:1:2, and the consumption of organic source of iron ferric oxalate is according to oxalate and the theoretical Li that generates 2FeP 2O 7Mass ratio 40% take by weighing, iron in shortage is supplied with inorganic source of iron di-iron trioxide.Reaction raw materials is placed ball grinder, add slurry drying under 100 ℃ that ethanol obtains behind ball mill mixing.Dried compound grind and compressing tablet after under nitrogen protection, rise to 400 ℃ and carry out predecomposition and handle 5h with the speed of 5 ℃/min; Material after predecomposition is handled grinds evenly and compressing tablet; Under the atmosphere identical with the predecomposition processing, rise to 800 ℃ of calcining 3h with the phase same rate then, cooling, grinding back products therefrom are Li 2FeP 2O 7Material.
Embodiment 3:
To analyze pure lithium acetate, ammonium phosphate and ferric acetate is lithium source, phosphorus source and source of iron.According to the Li:Fe:P mol ratio is the ratio weighing raw materials of 2:1:2, and the consumption of organic source of iron ferric acetate is according to acetate and the theoretical Li that generates 2FeP 2O 7Mass ratio 20% take by weighing, iron in shortage is supplied with inorganic source of iron iron hydroxide.Reaction raw materials is placed ball grinder, add slurry drying under 100 ℃ that ethanol obtains behind ball mill mixing.Dried compound grind and compressing tablet after rise to 300 ℃ with the speed of 3 ℃/min down hydrogen and argon gas mixed gas protected and carry out predecomposition processing 10h; Material after predecomposition is handled grinds evenly and compressing tablet; Under the atmosphere identical with the predecomposition processing, rise to 700 ℃ of calcining 12h with the phase same rate then, cooling, grinding back products therefrom are Li 2FeP 2O 7Material.
Embodiment 4:
To analyze pure lithium carbonate, diammonium hydrogen phosphate and ferric acetate is lithium source, phosphorus source and source of iron.According to the Li:Fe:P mol ratio is the ratio weighing raw materials of 2:1:2, and the consumption of organic source of iron ferric acetate is according to acetate and the theoretical Li that generates 2FeP 2O 7Mass ratio 30% take by weighing, iron in shortage is supplied with inorganic source of iron di-iron trioxide.Reaction raw materials is placed ball grinder, add slurry drying under 100 ℃ that ethanol obtains behind ball mill mixing.Dried compound grind and compressing tablet after rise to 250 ℃ with the speed of 2 ℃/min down hydrogen and argon gas mixed gas protected and carry out predecomposition processing 12h; Material after predecomposition is handled grinds evenly and compressing tablet; Under the atmosphere identical with the predecomposition processing, rise to 650 ℃ of calcining 15h with the phase same rate then, cooling, grinding back products therefrom are Li 2FeP 2O 7Material.
Embodiment 5:
To analyze pure lithium oxalate, ammonium phosphate and ironic citrate is lithium source, phosphorus source and source of iron.According to the Li:Fe:P mol ratio is the ratio weighing raw materials of 2:1:2, and organic source of iron ironic citrate consumption is according to citrate and the theoretical Li that generates 2FeP 2O 7Mass ratio 15% take by weighing, iron in shortage is supplied with inorganic source of iron iron iron hydroxide.Reaction raw materials is placed ball grinder, add slurry drying under 100 ℃ that ethanol obtains behind ball mill mixing.Dried compound grind and compressing tablet after under the protection of argon gas, rise to 350 ℃ and carry out predecomposition and handle 6h with the speed of 4 ℃/min; Material after predecomposition is handled grinds evenly and compressing tablet; Under the atmosphere identical with the predecomposition processing, rise to 750 ℃ of calcining 8h with the phase same rate then, cooling, grinding back products therefrom are Li 2FeP 2O 7Material.

Claims (6)

1. anode material for lithium-ion batteries Li 2FeP 2O 7The preparation method, it is characterized in that comprising following process:
1) with lithium source, inorganic source of iron, organic source of iron and phosphorus source, carry out weighing according to proportioning, use the ethanol mixing and ball milling then, the slurry that mixes is prepared calcining behind the compound process grinding that obtains, the compressing tablet after drying is removed ethanol;
2) the compressing tablet material that step 1) is obtained is put into calciner, pre-burning under protective atmosphere, and calcined temperature is 200～400 ℃; 5～15 hours pre-burning time, intensification degree rate is 1～5 ℃/min, at high temperature calcines behind the grinding of gained pre-burning material, the compressing tablet; Calcining heat is 600～800 ℃, and calcination time is 3～24 hours, and intensification degree rate is 1～5 ℃/min; Take out the calcining material then, obtain Li after the grinding 2FeP 2O 7Positive electrode;
Wherein proportioning raw materials is that the Li:Fe:P mol ratio is 2:1:2, and the consumption of organic source of iron is according to its contained organic acid and the theoretical Li that generates 2FeP 2O 7The mass ratio of required organic acid is 10%～40% to take by weighing, and iron in shortage is supplied with inorganic source of iron.
2. anode material for lithium-ion batteries Li as claimed in claim 1 2FeP 2O 7The preparation method, it is characterized in that: the lithium source described in the step 1) is lithium carbonate, lithium hydroxide, lithium oxalate or lithium acetate.
3. anode material for lithium-ion batteries Li as claimed in claim 1 2FeP 2O 7The preparation method, it is characterized in that the inorganic source of iron described in the step 1) is iron oxide, tri-iron tetroxide or iron hydroxide.
4. anode material for lithium-ion batteries Li as claimed in claim 1 2FeP 2O 7The preparation method, it is characterized in that the organic source of iron described in the step 1) is ironic citrate, ferric oxalate or ferric acetate.
5. anode material for lithium-ion batteries Li as claimed in claim 1 2FeP 2O 7The preparation method, it is characterized in that the phosphorus source described in the step 1) is diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.
6. anode material for lithium-ion batteries Li as claimed in claim 1 2FeP 2O 7The preparation method, it is characterized in that step 2) described in protective atmosphere be the mist of nitrogen, argon gas or hydrogen and argon gas.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000955A (en) * 2012-11-29 2013-03-27 陈小康 Preparation method of lithium ion battery for high-security mobile phone
CN103107332A (en) * 2013-01-24 2013-05-15 北大先行科技产业有限公司 LFP (lithium iron phosphate) positive electrode material with excellent low-temperature property and preparation method thereof
CN103825026A (en) * 2014-03-19 2014-05-28 中南大学 Method for preparing lithium iron pyrophosphate used as positive material for lithium ion battery
CN103985870A (en) * 2014-05-29 2014-08-13 中南大学 Method for synthesizing carbon-coated lithium ferrous pyrophosphate by hydrothermal method
CN105655539A (en) * 2014-11-10 2016-06-08 中国电子科技集团公司第十八研究所 Lithium ion battery positive electrode lithium iron pyrophosphate preparation method
CN107253707A (en) * 2013-09-04 2017-10-17 株式会社Lg 化学 Transition metal pyrophosphate negative electrode active material and the negative pole comprising it
CN110697673A (en) * 2019-10-15 2020-01-17 俞杰 Method for recycling regenerated lithium iron phosphate from waste power lithium ion battery
CN114394583A (en) * 2022-01-13 2022-04-26 上海太洋科技有限公司 Preparation method of titanium pyrophosphate slurry for lithium battery positive electrode material additive

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHIN-ICHI NISHIMURA,ET AL.: "New Lithium Iron Pyrophosphate as 3.5 V Class Cathode Material for Lithium Ion Battery", 《J. AM. CHEM. SOC》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000955A (en) * 2012-11-29 2013-03-27 陈小康 Preparation method of lithium ion battery for high-security mobile phone
CN103000955B (en) * 2012-11-29 2015-02-11 陈小康 Preparation method of lithium ion battery for high-security mobile phone
CN103107332A (en) * 2013-01-24 2013-05-15 北大先行科技产业有限公司 LFP (lithium iron phosphate) positive electrode material with excellent low-temperature property and preparation method thereof
CN103107332B (en) * 2013-01-24 2015-10-14 北大先行科技产业有限公司 A kind of lithium iron phosphate positive material and preparation method thereof
CN107253707A (en) * 2013-09-04 2017-10-17 株式会社Lg 化学 Transition metal pyrophosphate negative electrode active material and the negative pole comprising it
CN107253707B (en) * 2013-09-04 2019-12-13 株式会社Lg 化学 Transition metal-pyrophosphate negative electrode active material and negative electrode comprising same
CN103825026A (en) * 2014-03-19 2014-05-28 中南大学 Method for preparing lithium iron pyrophosphate used as positive material for lithium ion battery
CN103825026B (en) * 2014-03-19 2016-03-02 中南大学 A kind of method preparing anode material ferric pyrophosphate lithium of lithium ion battery
CN103985870A (en) * 2014-05-29 2014-08-13 中南大学 Method for synthesizing carbon-coated lithium ferrous pyrophosphate by hydrothermal method
CN105655539A (en) * 2014-11-10 2016-06-08 中国电子科技集团公司第十八研究所 Lithium ion battery positive electrode lithium iron pyrophosphate preparation method
CN110697673A (en) * 2019-10-15 2020-01-17 俞杰 Method for recycling regenerated lithium iron phosphate from waste power lithium ion battery
CN114394583A (en) * 2022-01-13 2022-04-26 上海太洋科技有限公司 Preparation method of titanium pyrophosphate slurry for lithium battery positive electrode material additive

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