CN101279728A - Method for preparing lithium iron phosphate cathode material by three-stage high-temperature solid phase calcination - Google Patents
Method for preparing lithium iron phosphate cathode material by three-stage high-temperature solid phase calcination Download PDFInfo
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- CN101279728A CN101279728A CNA2008100532756A CN200810053275A CN101279728A CN 101279728 A CN101279728 A CN 101279728A CN A2008100532756 A CNA2008100532756 A CN A2008100532756A CN 200810053275 A CN200810053275 A CN 200810053275A CN 101279728 A CN101279728 A CN 101279728A
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Abstract
The invention discloses a method for preparing lithium iron phosphate anode material by three-step high temperature solid state sintering and pertains to the technique of chemical power source anode material. The process of the preparation method is that lithium salt, Fe<2+> compound, phosphate and carbon source are mixed according to certain ratio, ground and granulated; particles obtained are transferred in a rotary sintering furnace and carried out predecomposition for 3-10 hours when the temperature is increased to 300-500 DEG C under the protection of nitrogen; the temperature raises to 650-850 DEG C and the heat is preserved for 6-15 hours and then the temperature is dropped to room temperature with furnace temperature; the material obtained is added with carbon source in different amount and is carried out ball milling, the temperature raises to 650-850 DEG C and the heat is preserved for 6-15 hours and then the temperature is dropped to room temperature with furnace temperature, and the lithium iron phosphate anode material is obtained after ball milling. The method of the invention is characterized by simple process, being easy to realize industrial scale production, wide sources of raw materials, low cost, complete crystal form of anode material, regular product pattern, excellent electrochemical performance and high tap density which reaches 1.36g cm<-3>.
Description
Technical field
The present invention relates to the method that a kind of three step high-temperature solid phase calcinations prepare lithium iron phosphate positive material, belong to chemical power source positive electrode material technical field.
Background technology
The survival and development of the energy and human society are of close concern to each other.Along with global population growth, rapid economic development, the energy is by mass consumption and caused the serious environmental pollution.In order to realize Sustainable development, must protect human physical environment and natural resources of depending on for existence, this is that the mankind enter the serious challenge that 21 century faces.
Chemical power source is a kind of device that chemical energy is converted into electric energy.Since R.G.Plante invention lead acid cell in 1859, G.Leclance in 1868 make zinc-manganse dioxide dry cell, chemical power source has experienced 100 years of development history, it has become in people's life uses convenient energy very widely, occupies crucial status in national economy and national defense industry.
Lithium ion battery is as the latest generation secondary cell, since nineteen ninety comes out development very rapid, in recent years, constantly replace lead-acid cell, nickel-cadmium cell and Ni-H cell in various different field.Nineteen ninety-five, the sales volume of nickel-cadmium cell accounts for 60% of whole miniature charging battery market, and Ni-H cell accounts for 29%, and lithium ion battery only accounts for 12%.By 2000, lithium ion battery rose to 55%, and Ni-H cell drops to 23%, and nickel-cadmium cell drops to 22%.Lithium ion battery further rose to 69% in 2003, and Ni-H cell drops to 10%, and nickel-cadmium cell drops to 20%.It is that the share that nickel-cadmium cell is still kept about 20% is because it is still the main product in power tool market owing to lose battery of mobile phone market that Ni-H cell sharply descends.According to statistics, world's lithium ion battery output was 12.55 hundred million in 2003, rose to 15.78 hundred million in 2004, and lithium ion battery output reached 2,600,000,000 in 2007, estimated that the average growth rate of 2007-2015 is 7%.The production of whole world lithium ion battery is based on Japanese firm, and Sony Corporation is maximum, also has SANYO, NEC, the LG of Korea S, SAMSUNG, the GS of the U.S., A﹠amp; Companies such as the BYD of T and Maxell and China, Bick, power god.Lithium ion battery is as the power supply renewal product, along with reaching its maturity and production-scale expansion of technology, lithium ion battery not only is applied to also will be widely used in electromobile, regional electronic comprehensive system, satellite and aerospace military field in portable electric appts such as mobile telephone, notebook computer, miniature camera and the memory support circuit.
The fast development of lithium ion battery depends on novel energy developing material and polytechnic progress.Positive electrode material is the key of lithium ion battery development.Being widely used in the small-scale lithium ion cell positive electrode material at present is cobalt acid lithium (LiCoO
2), but because the cobalt in the cobalt acid lithium is little at the reserves of occurring in nature, and the price comparison costliness has certain toxicity, and in the process of charging, cobalt acid lithium is because the embedding of taking off of metallic lithium becomes CoO
2, Co
4+Oxidisability is extremely strong, causes security incidents such as burning, blast easily.So high-power to developing, large vol needs the series-parallel power cell of a plurality of cells, adopt cobalt acid lithium to have huge potential safety hazard.Once lithium nickelate of being placed hopes on and lithium manganate did not have so far than quantum jump, LiNiO
2Though have higher capacity, in preparation, there is big difficulty, be difficult to the material of synthetic pure phase, and have certain safety problem.LiMn
2O
4Though low price, safety performance is good, and its theoretical capacity is not high, and cycle life, thermostability and high-temperature behavior are relatively poor.So these materials still are difficult to substitute cobalt acid lithium up to now.
Therefore, it is lower to continue to seek cost from resource, environmental protection and safety performance aspect, and chemical property is better, and the ideal electrode active material of the more friendly lithium ion battery of environment is still the challenge that quite a while international energy material interface from now on faces.
1997, reported first such as A.K.Padhi iron lithium phosphate (LiFePO
4) can embed and the removal lithium embedded ion by reversible, can serve as anode material for lithium-ion batteries, just caused people's extensive concern.The iron lithium phosphate raw material sources extensively, low price, nontoxic, environmentally friendly, theoretical specific capacity is high (about 170mAhg-1), compares with other lithium ion battery to have relative moderate operating voltage (3.4V, relative Li+/Li), has not only taken into account LiCoO
2, LiNiO
2And LiMn
2O
4The advantage of material, and thermally-stabilised good, safety performance is superior, cycle performance is outstanding, in numerous positive electrode materials, show one's talent, be considered to indicate " arrival of a New Times of lithium ion battery ", particularly become the preferred material of lithium ion power battery cathode material.
The content of invention
The object of the present invention is to provide a kind of three step high-temperature solid phase calcinations to prepare the method for lithium iron phosphate positive material, with the lithium iron phosphate positive material purity height that this method makes, the physicals and the electrochemistry of material are improved.
The present invention is realized that by the following technical programs a kind of three step high-temperature solid phase calcinations prepare the method for lithium iron phosphate positive material, it is characterized in that comprising following process:
1. will be selected from one or more the lithium salts in Quilonum Retard, lithium hydroxide, lithium oxalate and the Lithium Acetate, be selected from one or more the Fe in Ferrox, Iron nitrate or the ferrous phosphate
2+Compound, be selected from one or more the phosphoric acid salt in phosphoric acid hydrogen ammonia, ammonium di-hydrogen phosphate and the phosphoric acid ammonia, press lithium salts and Fe
2+Compound and phosphatic mol ratio 0.5: 1: 1 or mix at 1: 1: 1, press lithium salts and Fe again
2+Compound and phosphatic quality sum 2～4% add one or more the carbon source be selected from glucose, sucrose, carbon black, polyvinyl alcohol and the polyoxyethylene glycol, mix the wet method stirring ball-milling, the suspension liquid drying, the granulation that obtain obtain particulate material.
2. the particulate material that step 1 is obtained adds in the revolution sintering oven; under nitrogen protection atmosphere; furnace temperature rises to 300-500 ℃ of predecomposition 3-10 hour in 2～3 hours; rise to 650-850 ℃ in 2～3 hours furnace temperature again; be incubated after 6-15 hour furnace temperature and reduce to room temperature; take out particulate material; again to particulate material add with respect to the particulate material quality 2～4% be selected from glucose; sucrose; carbon black; the carbon source of one or more in polyvinyl alcohol and the polyoxyethylene glycol; obtaining median size through ball milling is 5 micro-powders; powder is added in the revolution sintering oven; under nitrogen protection atmosphere; furnace temperature rises to 650-850 ℃ in 3～4 hours; be incubated after 6-15 hour furnace temperature and reduce to room temperature, obtain lithium iron phosphate positive material behind the ball milling.
The lithium salts that said process is selected for use is Quilonum Retard or lithium hydroxide, the Fe of selecting and purchasing
2+Compound be Ferrox, the phosphoric acid salt of selecting and purchasing is phosphoric acid hydrogen ammonia or ammonium di-hydrogen phosphate.
The present invention has following outstanding feature: technology simply, control easily and operate, security and good stability are easily realized commercial scale production; Adopt the starting material wide material sources, cheap; Preparation positive electrode material complete in crystal formation, product pattern rule, chemical property is superior, and tap density has reached 1.36gcm
-3
Description of drawings:
Accompanying drawing 1 is the x-ray diffraction pattern of the lithium iron phosphate positive material of embodiment 1 preparation.Adopt the Rigaku-D/MAX-2550PC type x-ray powder diffraction instrument of HIT that the gained powdered sample is carried out material phase analysis, use Cu-K
αSource of radiation, wavelength is
Use the Ni filter plate, the Guan Liuwei 20mA of employing, pipe press and are 40KV, 4 °/min of sweep velocity, and step-length is 0.020 °.
Accompanying drawing 2 is sem photographs of the lithium iron phosphate positive material of embodiment 1 preparation.Adopt the SIKION type field emission scanning electron microscope of Dutch Philips-FEI company.
Accompanying drawing 3 is to be the different multiplying discharge curve of the battery of positive electrode material assembling with the iron lithium phosphate that embodiment 1 prepares.
Accompanying drawing 4 is to be the different multiplying cyclic curve figure of the battery of positive electrode material assembling with the iron lithium phosphate that embodiment 1 prepares.
Embodiment
Embodiment 1
With Li
2CO
3, FeC
2O
42H
2O and NH
4H
2PO
4By stoichiometric ratio weighing in 0.5: 1: 1, amount to 332 grams (Li wherein
2CO
3: 37 grams; FeC
2O
42H
2The O:180 gram; NH
4H
2PO
4: 115 grams), and adding is ground 5h with respect to glucose 13 grams of raw-material weight 4% in the wet method stirring ball mill.With the above-mentioned suspension liquid drying that obtains; granulation; the gained spherical particle is transferred in the revolution sintering oven, is warming up to 300 ℃ of predecomposition 5h under nitrogen protection atmosphere, is warming up to 750 ℃ again; reduce to room temperature with furnace temperature behind the insulation 12h; the gained sample adds with respect to raw-material weight 2% glucose again, behind the ball milling 12h, is warming up to 750 ℃ again; reduce to room temperature with furnace temperature behind the insulation 6h, obtain final iron lithium phosphate-carbon encapsulated material behind the ball milling 12h.Fig. 1 is the x-ray diffraction pattern of the iron lithium phosphate of embodiment 1 preparation, and Fig. 2 is the sem photograph of the iron lithium phosphate of embodiment 1 preparation.The median size D of iron lithium phosphate-carbon encapsulated material of surveying
50Be 2.1 μ m, tap density is 1.36gcm
-3
The matrix material of embodiment 1 gained is made battery as follows.
With the iron lithium phosphate-carbon encapsulated material and acetylene black (Super-P), electrically conductive graphite (KS-6), the polyvinylidene difluoride (PVDF) (HSV900) that obtain is 90: 3: 2 by weight: 5 mixed.Four kinds of material nominals are got 100 gram, wherein iron lithium phosphates: 90 grams; Acetylene black (Super-P): 3 grams; Electrically conductive graphite (KS-6): 2 grams; Polyvinylidene difluoride (PVDF): 5 grams.Obtain the positive plate that thickness is about 0.12mm after mixing compacting.With 1mol/LLiPF
6/ EC-DMC (v/v 1: 1) is an electrolytic solution, and barrier film is Celgard2300, is negative pole with the metallic lithium, is assembled into the CR2032 button cell.Utilize new prestige tester that the charge/discharge capacity and the cycle life of lithium iron phosphate positive material are tested.Fig. 3 be 0.2C, the 1C of ferric phosphate lithium cell of embodiment 1 preparation and 5C multiplying power discharging curve at room temperature, the scope of discharging and recharging is 2.0-3.8V.The result shows that 0.2C, 1C and the 5C specific discharge capacity of the iron lithium phosphate of embodiment 1 preparation are respectively 135.8mAhg
-1, 133.5mAhg
-1With 129.8mAhg
-1Fig. 4 be the ferric phosphate lithium cell of embodiment 1 preparation respectively with the cyclic curve of 0.2C, 1C and the circulation of 5C multiplying power discharging 20 times, after the result showed the circulation 20 times of the iron lithium phosphate that embodiment 1 prepares, 0.2C, 1C and 5C specific discharge capacity were respectively 135.0mAhg
-1, 132.7mAhg
-1With 129.0mAhg
-1, 20 capacity that circulate still keep 99.4%, and promptly each circulation loss capacity 0.03% shows excellent cycle performance and heavy-current discharge performance.
Embodiment 2
With Li
2CO
3, FeC
2O
42H
2O and (NH
4)
2HPO
4By stoichiometric ratio weighing in 0.5: 1: 1, amount to 332 grams (Li wherein
2CO
3: 37 grams; FeC
2O
42H
2The O:180 gram; NH
4H
2PO
4: 115 grams), and adding is ground 5h with respect to glucose 6.5 grams of raw-material weight 2% in the wet method stirring ball mill.With the above-mentioned suspension liquid drying that obtains; granulation; the gained spherical particle is transferred in the revolution sintering oven, is warming up to 300 ℃ of predecomposition 5h under nitrogen protection atmosphere, is warming up to 700 ℃ again; reduce to room temperature with furnace temperature behind the insulation 12h; the gained sample adds glucose 13 grams with respect to raw-material weight 4% again, behind the ball milling 12h, is warming up to 700 ℃ again; reduce to room temperature with furnace temperature behind the insulation 6h, obtain final iron lithium phosphate-carbon encapsulated material behind the ball milling 12h.The median size D of iron lithium phosphate-carbon encapsulated material of surveying
50Be 3.2 μ m, tap density is 1.32gcm
-3
Test by implementing 1 described step and operation assembled battery, 0.2C, 1C and the 5C specific discharge capacity of the iron lithium phosphate of embodiment 2 preparations of survey are respectively 132.4mAhg
-1, 128.7mAhg
-1With 124.1mAhg
-1Circulate after 20 times, 0.2C, 1C and 5C specific discharge capacity are respectively 131.4mAhg
-1, 127.6mAhg
-1With 122.8mAhg
-1
Embodiment 3
With LiOHH
2O, FeC
2O
42H
2O and (NH
4)
2HPO
4By stoichiometric ratio weighing in 1: 1: 1, amount to 337 grams (LiOHH wherein
2The O:42 gram; FeC
2O
42H
2The O:180 gram; NH
4H
2PO
4: 115 grams), in the wet method stirring ball mill, grind 5h.With the above-mentioned suspension liquid drying that obtains; granulation; the gained spherical particle is transferred in the revolution sintering oven, is warming up to 300 ℃ of predecomposition 5h under nitrogen protection atmosphere, is warming up to 650 ℃ again; reduce to room temperature with furnace temperature behind the insulation 12h; the gained sample adds glucose 20 grams with respect to raw-material weight 6% again, behind the ball milling 12h, is warming up to 650 ℃ again; reduce to room temperature with furnace temperature behind the insulation 6h, obtain final iron lithium phosphate-carbon encapsulated material behind the ball milling 12h.The median size D of iron lithium phosphate-carbon encapsulated material of surveying
50Be 3.8 μ m, tap density is 1.41gcm
-3
Test by implementing 1 described step and operation assembled battery, 0.2C, the 1C and the 5C specific discharge capacity that record the iron lithium phosphate of embodiment 3 preparations are respectively 125.7mAhg
-1, 121.2mAhg
-1With 116.0mAhg
-1Circulate after 20 times, 0.2C, 1C and 5C specific discharge capacity are respectively 124.7mAhg
-1, 119.3mAhg
-1With 112.7mAhg
-1
Claims (2)
1. one kind three goes on foot the method that high-temperature solid phase calcination prepares lithium iron phosphate positive material, it is characterized in that comprising following process:
1) will be selected from one or more lithium salts in Quilonum Retard, lithium hydroxide, lithium oxalate and the Lithium Acetate, be selected from one or more the Fe in Ferrox, Iron nitrate or the ferrous phosphate
2+Compound, be selected from one or more the phosphoric acid salt in phosphoric acid hydrogen ammonia, ammonium di-hydrogen phosphate and the phosphoric acid ammonia, press lithium salts and Fe
2+Compound and phosphatic mol ratio 0.5: 1: 1 or mix at 1: 1: 1, press lithium salts and Fe again
2+Compound and phosphatic quality sum 2～4% add one or more the carbon source be selected from glucose, sucrose, carbon black, polyvinyl alcohol and the polyoxyethylene glycol, mix the wet method stirring ball-milling, the suspension liquid drying, the granulation that obtain obtain particulate material;
2) particulate material that step 1) is obtained adds in the revolution sintering oven; under nitrogen protection atmosphere; furnace temperature rises to 300-500 ℃ of predecomposition 3-10 hour in 2～3 hours; rise to 650-850 ℃ in 2～3 hours furnace temperature again; be incubated after 6-15 hour furnace temperature and reduce to room temperature; take out particulate material; again to particulate material add with respect to the particulate material quality 2～4% be selected from glucose; sucrose; carbon black; the carbon source of one or more in polyvinyl alcohol and the polyoxyethylene glycol; obtaining median size through ball milling is 5 micro-powders; powder is added in the revolution sintering oven; under nitrogen protection atmosphere; furnace temperature rises to 650-850 ℃ in 3～4 hours; be incubated after 6-15 hour furnace temperature and reduce to room temperature, obtain lithium iron phosphate positive material behind the ball milling.
2. prepare the method for lithium iron phosphate positive material by the described three step high-temperature solid phase calcinations of claim 1, it is characterized in that the lithium salts of selecting for use is Quilonum Retard or lithium hydroxide, the Fe that selects for use
2+Compound be Ferrox, the phosphoric acid salt of selecting for use is phosphoric acid hydrogen ammonia or ammonium di-hydrogen phosphate.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985351A (en) * | 2010-09-30 | 2011-03-16 | 东南大学 | Method for preparing simple and cheap lithium-ion power battery anode materials |
| CN102115817A (en) * | 2011-03-23 | 2011-07-06 | 李浪航 | Laterite-nickel ore pelletizing sintering process |
| CN102126716A (en) * | 2011-03-01 | 2011-07-20 | 长沙理工大学 | Cathode material of lithium iron phosphate lithium battery and preparation method thereof |
| CN101764218B (en) * | 2010-01-12 | 2011-08-10 | 哈尔滨光宇电源股份有限公司 | Method for preparing cathode material of lithium iron phosphate lithium-ion battery |
| CN102354744A (en) * | 2011-10-08 | 2012-02-15 | 中国电子科技集团公司第十八研究所 | Method for improving stability in batch production of lithium iron phosphate |
| CN102544448A (en) * | 2010-12-30 | 2012-07-04 | 北京当升材料科技股份有限公司 | Method for preparing lithium battery positive electrode material |
| CN102633242A (en) * | 2012-04-27 | 2012-08-15 | 湖南恒平新材料科技有限公司 | Clearance-type one-step method for producing lithium iron phosphate |
| CN103022489A (en) * | 2012-12-31 | 2013-04-03 | 北京天奈科技有限公司 | Carbon nano tube phosphate lithium-embedded cathode material with low specific surface area and preparation method thereof |
| CN103178244A (en) * | 2011-12-23 | 2013-06-26 | 财团法人工业技术研究院 | Hybrid energy storage element |
| CN103985862A (en) * | 2014-04-14 | 2014-08-13 | 江苏中欧材料研究院有限公司 | Synthetic method of high vibration compaction high specific capacity phosphatic positive pole material |
| CN107359342A (en) * | 2017-07-27 | 2017-11-17 | 泓辰电池材料有限公司 | Lithium phosphate ferromanganese system particle, lithium phosphate ferromanganese system powder and preparation method thereof |
| CN111410239A (en) * | 2020-03-20 | 2020-07-14 | 广东顺德工业设计研究院(广东顺德创新设计研究院) | Regeneration and recovery method of retired nickel cobalt lithium manganate battery positive electrode material |
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2008
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| CN101764218B (en) * | 2010-01-12 | 2011-08-10 | 哈尔滨光宇电源股份有限公司 | Method for preparing cathode material of lithium iron phosphate lithium-ion battery |
| CN101985351A (en) * | 2010-09-30 | 2011-03-16 | 东南大学 | Method for preparing simple and cheap lithium-ion power battery anode materials |
| CN102544448A (en) * | 2010-12-30 | 2012-07-04 | 北京当升材料科技股份有限公司 | Method for preparing lithium battery positive electrode material |
| CN102126716A (en) * | 2011-03-01 | 2011-07-20 | 长沙理工大学 | Cathode material of lithium iron phosphate lithium battery and preparation method thereof |
| CN102115817B (en) * | 2011-03-23 | 2012-11-28 | 李浪航 | Laterite-nickel ore pelletizing sintering process |
| CN102115817A (en) * | 2011-03-23 | 2011-07-06 | 李浪航 | Laterite-nickel ore pelletizing sintering process |
| CN102354744A (en) * | 2011-10-08 | 2012-02-15 | 中国电子科技集团公司第十八研究所 | Method for improving stability in batch production of lithium iron phosphate |
| CN103178244A (en) * | 2011-12-23 | 2013-06-26 | 财团法人工业技术研究院 | Hybrid energy storage element |
| CN102633242A (en) * | 2012-04-27 | 2012-08-15 | 湖南恒平新材料科技有限公司 | Clearance-type one-step method for producing lithium iron phosphate |
| CN103022489A (en) * | 2012-12-31 | 2013-04-03 | 北京天奈科技有限公司 | Carbon nano tube phosphate lithium-embedded cathode material with low specific surface area and preparation method thereof |
| CN103022489B (en) * | 2012-12-31 | 2015-11-25 | 北京天奈科技有限公司 | Embedding lithium anode material of low specific surface area carbon nano-tube phosphoric acid salt and preparation method thereof |
| CN103985862A (en) * | 2014-04-14 | 2014-08-13 | 江苏中欧材料研究院有限公司 | Synthetic method of high vibration compaction high specific capacity phosphatic positive pole material |
| CN107359342A (en) * | 2017-07-27 | 2017-11-17 | 泓辰电池材料有限公司 | Lithium phosphate ferromanganese system particle, lithium phosphate ferromanganese system powder and preparation method thereof |
| CN107359342B (en) * | 2017-07-27 | 2019-12-24 | 泓辰电池材料有限公司 | Lithium ferromanganese phosphate particles and lithium ferromanganese phosphate powder |
| CN111410239A (en) * | 2020-03-20 | 2020-07-14 | 广东顺德工业设计研究院(广东顺德创新设计研究院) | Regeneration and recovery method of retired nickel cobalt lithium manganate battery positive electrode material |
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Application publication date: 20081008 Assignee: Hubei Baijierui Advanced Materials Co., Ltd. Assignor: Tianjin University Contract record no.: 2012120000063 Denomination of invention: Method for preparing lithium iron phosphate cathode material by three-stage high-temperature solid phase calcination Granted publication date: 20100908 License type: Exclusive License Record date: 20121009 |
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Granted publication date: 20100908 Termination date: 20210528 |
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| CF01 | Termination of patent right due to non-payment of annual fee |