CN102751498B - 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 PDFInfo
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- CN102751498B CN102751498B CN201210255197.4A CN201210255197A CN102751498B CN 102751498 B CN102751498 B CN 102751498B CN 201210255197 A CN201210255197 A CN 201210255197A CN 102751498 B CN102751498 B CN 102751498B
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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
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- Y02E60/10—Energy storage using batteries
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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
Technical field
The present invention relates to a kind of preparation method of anode material ferric pyrophosphate lithium of lithium ion battery, belong to new energy materials field.
Background technology
Chemical power source (battery) is a kind of is the device of electric energy by chemical reaction by converts chemical energy; it is one of important way of energy storage and conversion; being widely used in the daily life of industry, the military and mankind, is the important tool alleviated current energy crisis and reduce environmental pollution.
In the secondary battery, lithium ion battery due to have operating voltage high, have extended cycle life, capacity is large, volume is little, self discharge is little, the advantages such as few are polluted in memory-less effect and environmental protection, becomes rapidly the first-selection of current portable type electronic product rechargeable.For lithium ion battery, positive electrode has conclusive effect to its capacity, and closely bound up with the cost of battery, security performance, positive electrode oneself become the key factor that restriction lithium ion battery overall performance improves further.Therefore, the exploitation of Olivine-type Cathode Material in Li-ion Batteries 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) middle report employing divalence source of iron, synthesize a kind of anode material for lithium-ion batteries Li of Novel phosphoric acid salt system
2feP
2o
7.This material has the voltage platform of about 3.5V, and theoretical capacity is high, good cycle.Because divalence source of iron is expensive, 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
7preparation method, Li obtained in this way
2feP
2o
7positive electrode purity is high, and the electrochemistry capacitance of material is high, good cycle.
The object of the invention is to be achieved through the following technical solutions.
A kind of anode material for lithium-ion batteries Li
2feP
2o
7preparation method, comprise following process:
1) by lithium source, inorganic source of iron, organic source of iron and phosphorus source, weigh according to proportioning, then use ethanol mixing and ball milling, after the slurry drying removing ethanol mixed, the compound obtained prepares calcining after grinding, compressing tablet;
2) by step 1) the compressing tablet material that obtains puts into calciner; pre-burning under protective atmosphere; calcined temperature is 200 ~ 400 DEG C, burn-in time 5 ~ 15 hours, and intensification degree rate is 1 ~ 5 DEG C/min; at high temperature calcine after gained pre-burning ground material, compressing tablet; calcining heat is 600 ~ 800 DEG C, and calcination time is 3 ~ 24 hours, and intensification degree rate is 1 ~ 5 DEG C/min; then take out calcining material, after grinding, obtain Li
2feP
2o
7positive electrode;
Wherein pulp furnish is Li:Fe:P mol ratio is 2:1:2, and the consumption of organic source of iron is according to organic acid contained by it and the theoretical Li generated
2feP
2o
7the mass ratio of required organic acid is 10% ~ 40% to take, and iron in shortage is supplied with inorganic source of iron.
Above-mentioned steps 1) described in lithium source be lithium carbonate, lithium hydroxide, lithium oxalate or lithium acetate.
Above-mentioned steps 1) described in inorganic source of iron be iron oxide, tri-iron tetroxide or iron hydroxide.
Above-mentioned steps 1) described in organic source of iron be ironic citrate, ferric oxalate or ferric acetate.
Above-mentioned steps 1) described in phosphorus source be diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.
Above-mentioned steps 2) described in protective atmosphere be 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
7technique simply, easily realize industrial-scale production; Raw material sources is extensive, cheap.
Accompanying drawing explanation
Fig. 1 is for embodiment 1 gained sample Li
2feP
2o
7xRD image
Fig. 2 is for embodiment 1 gained sample Li
2feP
2o
7sEM image (amplifying 5000 times)
Fig. 3 is for embodiment 1 gained sample Li
2feP
2o
7sEM image (amplifying 20000 times)
Fig. 4 is for embodiment 1 gained sample gained first charge-discharge curve.
Embodiment
Be described in detail the present invention below by specific embodiment, following embodiment is only for illustration of the present invention, but the practical range be not intended to limit the present invention.
Embodiment 1:
To analyze, pure lithium carbonate, ammonium dihydrogen phosphate and ironic citrate are lithium source, phosphorus source and source of iron.According to the ratio weighing raw materials that Li:Fe:P mol ratio is 2:1:2, the consumption of organic source of iron ironic citrate generates Li according to citrate with theoretical
2feP
2o
7mass ratio 10% take, iron in shortage is supplied with inorganic source of iron tri-iron tetroxide.Reaction raw materials is placed in ball grinder, adds slurry drying at 100 DEG C that ethanol obtains after ball mill mixing.Dried compound grinds and under argon shield, rises to 200 DEG C with the speed of 1 DEG C/min after compressing tablet and carries out predecomposition process 15h; the even also compressing tablet of ground material after predecomposition process; then under the atmosphere identical with predecomposition process, rise to 600 DEG C with phase same rate and calcine 24h, after cooling, grinding, products therefrom is Li
2feP
2o
7material.
Embodiment 2:
To analyze, pure lithium oxalate, diammonium hydrogen phosphate and ferric oxalate are lithium source, phosphorus source and source of iron.According to the ratio weighing raw materials that Li:Fe:P mol ratio is 2:1:2, the consumption of organic source of iron ferric oxalate generates Li according to oxalate with theoretical
2feP
2o
7mass ratio 40% take, iron in shortage is supplied with inorganic source of iron di-iron trioxide.Reaction raw materials is placed in ball grinder, adds slurry drying at 100 DEG C that ethanol obtains after ball mill mixing.Dried compound grinds and rises to 400 DEG C with the speed of 5 DEG C/min under nitrogen protection after compressing tablet and carries out predecomposition process 5h; the even also compressing tablet of ground material after predecomposition process; then under the atmosphere identical with predecomposition process, rise to 800 DEG C with phase same rate and calcine 3h, after cooling, grinding, products therefrom is Li
2feP
2o
7material.
Embodiment 3:
To analyze, pure lithium acetate, ammonium phosphate and ferric acetate are lithium source, phosphorus source and source of iron.According to the ratio weighing raw materials that Li:Fe:P mol ratio is 2:1:2, the consumption of organic source of iron ferric acetate generates Li according to acetate with theoretical
2feP
2o
7mass ratio 20% take, iron in shortage is supplied with inorganic source of iron iron hydroxide.Reaction raw materials is placed in ball grinder, adds slurry drying at 100 DEG C that ethanol obtains after ball mill mixing.The grinding of dried compound and after compressing tablet hydrogen and argon gas mixed gas protected under rise to 300 DEG C with the speed of 3 DEG C/min and carry out predecomposition process 10h; the even also compressing tablet of ground material after predecomposition process; then under the atmosphere identical with predecomposition process, rise to 700 DEG C with phase same rate and calcine 12h, after cooling, grinding, products therefrom is Li
2feP
2o
7material.
Embodiment 4:
To analyze, pure lithium carbonate, diammonium hydrogen phosphate and ferric acetate are lithium source, phosphorus source and source of iron.According to the ratio weighing raw materials that Li:Fe:P mol ratio is 2:1:2, the consumption of organic source of iron ferric acetate generates Li according to acetate with theoretical
2feP
2o
7mass ratio 30% take, iron in shortage is supplied with inorganic source of iron di-iron trioxide.Reaction raw materials is placed in ball grinder, adds slurry drying at 100 DEG C that ethanol obtains after ball mill mixing.The grinding of dried compound and after compressing tablet hydrogen and argon gas mixed gas protected under rise to 250 DEG C with the speed of 2 DEG C/min and carry out predecomposition process 12h; the even also compressing tablet of ground material after predecomposition process; then under the atmosphere identical with predecomposition process, rise to 650 DEG C with phase same rate and calcine 15h, after cooling, grinding, products therefrom is Li
2feP
2o
7material.
Embodiment 5:
To analyze, pure lithium oxalate, ammonium phosphate and ironic citrate are lithium source, phosphorus source and source of iron.According to the ratio weighing raw materials that Li:Fe:P mol ratio is 2:1:2, organic source of iron ironic citrate consumption generates Li according to citrate with theoretical
2feP
2o
7mass ratio 15% take, iron in shortage is supplied with inorganic source of iron iron iron hydroxide.Reaction raw materials is placed in ball grinder, adds slurry drying at 100 DEG C that ethanol obtains after ball mill mixing.Dried compound grinds and under the protection of argon gas, rises to 350 DEG C with the speed of 4 DEG C/min after compressing tablet and carries out predecomposition process 6h; the even also compressing tablet of ground material after predecomposition process; then under the atmosphere identical with predecomposition process, rise to 750 DEG C with phase same rate and calcine 8h, after cooling, grinding, products therefrom is Li
2feP
2o
7material.
Claims (4)
1. an anode material for lithium-ion batteries Li
2feP
2o
7preparation method, it is characterized in that comprising following process:
1) by lithium source, inorganic source of iron, organic source of iron and phosphorus source, weigh according to proportioning, then use ethanol mixing and ball milling, after the slurry drying removing ethanol mixed, the compound obtained prepares calcining after grinding, compressing tablet;
2) by step 1) the compressing tablet material that obtains puts into calciner; pre-burning under protective atmosphere; calcined temperature is 200 ~ 400 DEG C, burn-in time 5 ~ 15 hours, and intensification degree rate is 1 ~ 5 DEG C/min; at high temperature calcine after gained pre-burning ground material, compressing tablet; calcining heat is 600 ~ 800 DEG C, and calcination time is 3 ~ 24 hours, and intensification degree rate is 1 ~ 5 DEG C/min; then take out calcining material, after grinding, obtain Li
2feP
2o
7positive electrode;
Wherein pulp furnish is Li:Fe:P mol ratio is 2:1:2, and the consumption of organic source of iron is according to organic acid contained by it and the theoretical Li generated
2feP
2o
7the mass ratio of required organic acid is 10% ~ 40% to take, iron in shortage is supplied with inorganic source of iron, inorganic source of iron described in step 1) is iron oxide, tri-iron tetroxide or iron hydroxide, and the organic source of iron described in step 1) is ironic citrate, ferric oxalate or ferric acetate.
2. anode material for lithium-ion batteries Li as claimed in claim 1
2feP
2o
7preparation method, it is characterized in that: the lithium source described in 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
7preparation method, it is characterized in that, the phosphorus source described in step 1) is diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate.
4. anode material for lithium-ion batteries Li as claimed in claim 1
2feP
2o
7preparation 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103000955B (en) * | 2012-11-29 | 2015-02-11 | 陈小康 | Preparation method of lithium ion battery for high-security mobile phone |
| 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 |
| CN104662717B (en) * | 2013-09-04 | 2018-01-02 | 株式会社Lg 化学 | Transition metal pyrophosphate negative electrode active material and preparation method thereof, the lithium secondary battery or mixed capacitor for including it |
| 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 |
| CN103985870B (en) * | 2014-05-29 | 2016-03-02 | 中南大学 | The method of the coated ferrous pyrophosphate lithium of a kind of hydrothermal synthesis of carbon |
| 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 |
| CN110697673B (en) * | 2019-10-15 | 2021-01-12 | 徐州西迈斯能源科技有限公司 | 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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