CN102910611A - Method for preparing ferrous phosphate-based lithium salt - Google Patents
Method for preparing ferrous phosphate-based lithium salt Download PDFInfo
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- CN102910611A CN102910611A CN2012103930323A CN201210393032A CN102910611A CN 102910611 A CN102910611 A CN 102910611A CN 2012103930323 A CN2012103930323 A CN 2012103930323A CN 201210393032 A CN201210393032 A CN 201210393032A CN 102910611 A CN102910611 A CN 102910611A
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Abstract
The invention relates to a method for preparing a lithium iron phosphate material through a solvothermal method, in particular to a method for preparing a ferrous phosphate-based lithium salt. The method is characterized by comprising the following steps of: (1) preparing primary nano-grade lithium iron phosphate particles; (2) atomizing to form secondary particles; and (3) sintering lithium iron phosphate: sintering the obtained secondary lithium iron phosphate particles, baking in a nitrogen atmosphere or a mixed atmosphere of nitrogen and hydrogen in the volume ratio of (1-5):(95-99) at the high temperature of 400-800 DEG C for 6-25 hours, and cooling. The method for preparing the ferrous phosphate-based lithium salt provided by the invention has the advantages of rich raw material source, low price, simple and practicable synthesizing process, safety, reliability, low production cost, high yield and freeness from environmental pollution; and a product has high electrochemical performance. A high-boiling-point solvent is adopted partially instead of water, so that preparation of nano-grade lithium iron phosphate through a normal-pressure low-temperature hydrothermal method is realized.
Description
Technical field
The present invention relates to solvent-thermal method and prepare LiFePO 4 material, especially a kind of method for preparing the ferrous phosphate radical lithium salts.
Background technology
Prior art generally adopts solid phase method or wet chemical method to prepare positive active material LiFePO
4, for example Chinese patent CN 1401559A discloses a kind of iron lithium phosphate (LiFePO
4) the preparation method, the method with lithium salts, ferrous salt and phosphoric acid salt ground and mixed evenly after high-temperature calcination, calcine complete rear adding conductive agent ground and mixed and make iron lithium phosphate.But during the employing solid phase method, various solids components are difficult to fully mix, and especially the conductive agent dispersion is inhomogeneous for various compositions in the iron phosphate lithium positive pole active substance that therefore obtains, and directly affects the electroconductibility of positive active material.
Hydro-thermal prepares iron lithium phosphate and needs high-temperature high-pressure apparatus, under the aqueous solution, temperature is greater than 160 degree and could reacts, and safety and continuous industry production are had larger challenge, mainly is that P2 model and the Korea S Han Hua chemistry of Canadian south chemistry adopts hydrothermal method production in the world.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the ferrous phosphate radical lithium salts, the method raw material sources are abundant, cheap, and synthesis technique is simple.
A kind of method for preparing the ferrous phosphate radical lithium salts, its special feature is, comprises the steps:
(1) preparation nano-scale lithium iron phosphate primary particle:
Take by weighing phosphoric acid salt, molysite, three kinds of raw materials of lithium salts, it is P: Fe: Li=1 according to molar ratio: 0.7～1.3: 2～4 ratio, be dissolved in water to 0.5～2mol/L, then lithium salts and phosphoric acid salt are mixed mutually, add again molysite after the formation precipitation to be mixed, after stirring 0.5-2h under the 200-600r/min, solution poured in the container heat, add simultaneously the high boiling organic solvent that accounts for mixed liquor volume 50%～80%, then the S-WAT that adds mixing solutions quality 0.5～2%, be that the pH value that 15%～40% ammoniacal liquor is regulated mixed reaction solution is 6.5～7.5 by adding 0.1～2mol/L lithium hydroxide or concentration again, Heating temperature remains on 100-120 ℃, then through 3～5 filtration washings, obtain lithium iron phosphate nano particle until flocks is formed on the bottom 1-5 hour heat-up time;
(2) spraying forms offspring:
The lithium iron phosphate nano particle that obtains is mixed according to mass ratio 1:1～1.5 with water, and the organic carbon source of adding iron lithium phosphate precursor mass ratio 10～30%, then use spray drying unit to spray, 130-180 ℃ of device inlet temperature, temperature out 50-100 ℃, obtain the iron lithium phosphate second particle; (3) iron lithium phosphate sintering:
The iron lithium phosphate second particle that obtains is carried out sintering, in nitrogen atmosphere or nitrogen and the mixed atmosphere of hydrogen with volume ratio 1-5: 95-99, through 400-800 ℃ high-temperature roasting 6-25 hour then the cooling get final product.
Utilizing magnetic stirring apparatus to stir behind adding lithium salts and the phosphoric acid salt in the step (1) fully dissolves it.
Step (1) Raw lithium salts adopts Quilonum Retard, lithium hydroxide or lithium fluoride; Molysite adopts Iron diacetate, Iron nitrate, iron protochloride or ferrous sulfate; Phosphoric acid salt adopts monometallic, primary ammonium phosphate, triammonium phosphate or phosphoric acid.
High boiling organic solvent adopts methyl-sulphoxide, different fluorine that ketone or PBE in the step (1).
Organic carbon source adopts glucose, sucrose or polyvinyl alcohol in the step (2).
The invention provides a kind of method for preparing the ferrous phosphate radical lithium salts, used raw material sources are abundant, cheap, and synthesis technique is simple, safe and reliable, production cost is low, productive rate is high, and non-environmental-pollution, product have better chemical property.The present invention partly replaces water with high boiling organic solvent, has realized that the atmospheric low-temperature hydrothermal method prepares nano-scale lithium iron phosphate.
Description of drawings
Fig. 1 is scanning electron microscope (SEM) photograph (SEM) figure of the iron lithium phosphate of example 1 preparation;
Fig. 2 is scanning electron microscope (SEM) photograph (SEM) figure of the iron lithium phosphate of example 2 preparations;
Fig. 3 is scanning electron microscope (SEM) photograph (SEM) figure of the iron lithium phosphate of example 3 preparations
Fig. 4 is scanning electron microscope (SEM) photograph (SEM) figure of the iron lithium phosphate of example 3 preparations
Fig. 5 is X-ray diffraction (XRD) figure of the iron lithium phosphate of example 1 preparation;
Fig. 6 is X-ray diffraction (XRD) figure of the iron lithium phosphate of example 2 preparations;
Fig. 7 is X-ray diffraction (XRD) figure of the iron lithium phosphate of example 3 preparations;
Fig. 8 is X-ray diffraction (XRD) figure of the iron lithium phosphate of example 3 preparations.
Embodiment
The present invention proposes a kind of method that is applicable to the synthesis nano iron lithium phosphate:
(1) preparation nano-scale lithium iron phosphate primary particle:
Take by weighing phosphoric acid salt, molysite, three kinds of raw materials of lithium salts, it is P: Fe: Li=1 according to molar ratio: 0.7～1.3: 2～4 ratio, be dissolved in water to 0.5～2mol/L, then lithium salts and phosphoric acid salt are mixed mutually, add molysite after the formation to be mixed precipitation, through after stirring 0.5-2h under the 200-800r/min and stirring, solution poured in the container heat, then the high boiling organic solvent that adds simultaneously mixed liquor volume 50%～80% adds mixing solutions quality 0.5～2% S-WAT;
Adding organic solvent is for improving the boiling point of mixing liquid, is that antioxidant suppresses Fe with S-WAT
2+Oxidation, be that the pH value that 15%～40% ammoniacal liquor is regulated mixed reaction solution is 6.5～7.5 by adding 0.1～2mol/L lithium hydroxide or concentration again, Heating temperature remains on 100-120 ℃, 1-5 hour heat-up time is until flocks is formed on the bottom, then through 3～5 filtration washings, obtain the lithium iron phosphate nano particle;
(2) spraying forms offspring:
The synthetic lithium iron phosphate nano particle that obtains is mixed according to mass ratio 1:1～1.5 with water, and adding iron lithium phosphate precursor mass ratio 10～30% organic carbon sources, then use spray drying unit to spray, 130-180 ℃ of device inlet temperature, temperature out 50-100 ℃, obtain the iron lithium phosphate second particle; And be shaped as sphere, and size is even, fine powder content is low.
(3) iron lithium phosphate sintering:
Utilize the atmosphere tube type stove that iron lithium phosphate is carried out sintering, nitrogen or hydrogen is a kind of or two kinds of mixed gas inert environments in, through 400-800 ℃ high-temperature roasting 6-25 hour, obtain lithium iron phosphate positive material.
The inventive method is that other raw material of molecular level mixes, reaction evenly, and the particle that forms is nano level, is beneficial to lithium ion turnover iron lithium phosphate offspring.
The present invention adopts spray-dired purpose for obtaining spheroidal particle, can improve the tap density of positive electrode material because of spheroidal particle, optimizes the coating processes of making battery process.
Important improvement point of the present invention is: by traditional hydrothermal method high boiling organic solvent Substitute For Partial water, realize that solvent thermal prepares iron lithium phosphate under the high-temperature pressure in the technique, greatly reduce the processing unit requirement, eliminate the potential safety hazard of high-tension apparatus.
Raw material in the technique adopts ferrous salt, because of the characteristic of its unstable easy oxidation, the purity that obtains iron lithium phosphate is had a significant impact, and carries out ferrous oxidation inhibition by adding antioxidant.The synthetic commonly used antioxidant of iron lithium phosphate was xitix in the past, but by, find that its anti-oxidation characteristics is undesirable, utilize S-WAT fine as antioxidant effect, product purity has very large lifting through test.
The present invention mixes the formation precipitation with phosphoric acid salt and lithium salts first in the batch mixing process, then add ferrous salt and organic solvent, meets the ultimate principle that hydro-thermal prepares iron lithium phosphate, i.e. Fe
2++ Li
3PO
4=LiFePO
4+ 2Li
+Could realize that low temperature prepares iron lithium phosphate.When the present invention mixed three kinds of raw materials, the mixing velocity that liquid shifts was influential to the size distribution of product, should try one's best and slowly pour into.Mechanical stirring intensity during oil bath is influential to ultimate size equally, should improve rotating speed and reduces Nano Particle.
When the recovery of the organic solvent that the present invention uses is purified, note reclaiming the purity test of solvent, utilize refractometer or high performance liquid chromatography to measure, filter simultaneously the inorganic salt impurity of removing precipitation.
Embodiment 1:
Utilize analytical balance accurately to take by weighing respectively (NH
4)
3PO
4Be 149g, FeCl
2Be 126.9g, LiF is 78g, is dissolved in respectively in the 500ml water, the mechanical stirring rotating speed is set is 300r/min and fully dissolve and mix.Stirred 20 minutes, raw material dissolves fully, without vision visible crystal grain.At this moment, under mechanical stirring slurry (rotating speed=400 rev/min) effect, while stirring first with (NH
4)
3PO
4Pour large round bottom flask into two kinds of solution that prepare of LiF, stir 30min, then add FeCl
2, add simultaneously methyl-sulphoxide 1500m1, add S-WAT 6.54g as antioxidant, adding concentration is the Ph=6.5 of 1mol/L lithium hydroxide regulator solution.Utilize 104 ℃ of lower heating 2h of oil bath (this example use silicone oil), in heating, utilize mechanical stirrer (rotating speed=400 rev/min) to stir, after finishing the solid of drag is carried out 3 times and filter and washing, finally obtain presoma.
The water that filtration is obtained and the mixing solutions of methyl-sulphoxide are poured Rotary Evaporators into, and vacuum tightness is-0.09MPa, and when temperature reaches 70 ℃, water begins violent boiling and steams, and keeps temperature 6 hours, and moisture is separated fully.To not steam liquid filtering and remove precipitation and sl. sol. inorganic salt, the methyl-sulphoxide that obtains utilizes refractometer to carry out purity test, can be used as organic solvent and reuse when making the coprecipitation reaction of iron lithium phosphate next time.
The 200g presoma is dissolved in 200g water, adds the dissolving of 30g glucose again and mix, spraying obtains second particle, and spraying machine is set spray parameters, 140 ℃ of inlet temperatures, and 70 ℃ of temperature outs obtain the iron lithium phosphate second particle.
Place tube furnace to carry out roasting second particle, in tube furnace, pass into the mixed gas of 90% nitrogen and 10% hydrogen, be warmed up to 800 ℃ with the speed of 2 ℃/min, keep temperature 6h, treat that stove naturally cools to room temperature, obtain the ball shape ferric phosphate lithium material.
LiFePO 4 material is carried out SEM detect, it is even that pattern can get the offspring particle diameter, and segmentation is few, and particle is spherical, can effectively increase tap density.
Embodiment 2:
Utilize analytical balance accurately to take by weighing respectively H
3PO
4Be 9.8g, FeSO
4Be 15.2g, LiOH is 7.2g, is dissolved in respectively in the 50ml water, the mechanical stirring rotating speed is set is 200r/min and stir and fully dissolve and mix.Treat that medicine dissolves fully, without visible crystals particle vision as seen.At this moment, under mechanical stirring slurry (rotating speed=300 rev/min) effect, while stirring first with H
3PO
4Pour large round bottom flask into two kinds of solution that prepare of LiOH, stir 30min, then add FeSO
4, add simultaneously methyl-sulphoxide 150ml, add S-WAT 0.65g as antioxidant, utilize the Ph=7 of concentration 30% ammoniacal liquor regulator solution.Utilize 110 ℃ of lower heating 4h of oil bath (this laboratory use silicone oil), in heating, utilize mechanical stirrer (rotating speed=300 rev/min) to stir simultaneously, the solid of drag is carried out filtration washing 4 times, finally obtain presoma.
The water that filtration obtains and the mixing solutions of methyl-sulphoxide are poured Rotary Evaporators into, and vacuum tightness is-0.09MPa, and when temperature reaches 70 ℃, water begins violent boiling and steams, and keeps temperature 6 hours, and moisture is separated fully.To not steam liquid filtering and remove precipitation and sl. sol. inorganic salt, the pure methyl-sulphoxide that obtains utilizes refractometer to carry out purity test, makes the coprecipitation reaction of iron lithium phosphate in next time and reuses as organic solvent.
10g presoma and 2g glucose is dissolved in spraying behind the 20g water obtains second particle, spraying machine is set spray parameters, 180 ℃ of inlet temperatures, and 60 ℃ of temperature outs obtain the iron lithium phosphate second particle.
Place tube furnace to carry out roasting second particle, pass into nitrogen protection gas in tube furnace, be warmed up to 700 ℃ with the speed of 10 ℃/min, keep temperature 12h, stove naturally cools to room temperature, obtains the ball shape ferric phosphate lithium material.
LiFePO 4 material is carried out SEM detect, it is even that pattern can get the offspring particle diameter, and segmentation is few, and particle is spherical, can effectively increase tap density.
Embodiment 3:
Utilize analytical balance accurately to take by weighing respectively H
3PO
4Be 9.8g, FeSO
4Be 15.2g, LiOH is 7.2g, is dissolved in respectively in the 50ml water, the mechanical stirring rotating speed is set is 500r/min and fully dissolve and mix.Treat that medicine dissolves fully, without visible crystals particle vision as seen.At this moment, under mechanical stirring slurry (rotating speed=400 rev/min) effect, while stirring first with H
3PO
4Pour large round bottom flask into two kinds of solution that prepare of LiOH, stir 30min, then add FeSO
4, add simultaneously different fluorine that ketone 150ml, add S-WAT 0.65g as antioxidant, be the Ph=6.8 of 15% ammoniacal liquor regulator solution with concentration.Utilize 140 ℃ of lower heating 10h of oil bath (this laboratory use silicone oil), in heating, utilize mechanical stirrer (rotating speed=600 rev/min) to stir simultaneously, the solid of drag is repeatedly cleaned and filters, finally obtain presoma.
You pour Rotary Evaporators into by the mixing solutions of ketone the water that filtration obtains and different fluorine, and vacuum tightness be-0.09MPa, and when temperature reaches 70 ℃, water begins violent boiling and steams, maintenance temperature 6 hours, and moisture is separated fully.To not steam liquid filtering and remove precipitation and sl. sol. inorganic salt, your ketone of different fluorine that obtains utilizes refractometer to carry out purity test, makes the coprecipitation reaction of iron lithium phosphate in next time and reuses as organic solvent.
15g presoma and 3g sucrose is dissolved in spraying behind the 15g water obtains second particle, spraying machine is set spray parameters, 150 ℃ of inlet temperatures, and 65 ℃ of temperature outs obtain the iron lithium phosphate second particle.
Place tube furnace to carry out roasting second particle, pass into the mixed gas of 97% nitrogen and 3% hydrogen in tube furnace, be warmed up to 750 ℃ with the speed of 5 ℃/min, keep temperature 10h, stove naturally cools to room temperature, obtains the ball shape ferric phosphate lithium material.
LiFePO 4 material is carried out SEM detect, it is even that pattern can get the offspring particle diameter, and segmentation is few, and particle is spherical, can effectively increase tap density.
Embodiment 4:
Utilize analytical balance accurately to take by weighing respectively H
3PO
4Be 9.8g, FeSO
4Be 15.2g, LiOH is 7.2g, is dissolved in respectively in the 50ml water, the mechanical stirring rotating speed is set is 400r/min and fully dissolve and mix.Treat that medicine dissolves fully, without visible crystals particle vision as seen.At this moment, under mechanical stirring slurry (rotating speed=300 rev/min) effect, while stirring first with H
3PO
4Pour large round bottom flask into two kinds of solution that prepare of LiOH, stir 30min, then add FeSO
4, add simultaneously the PBE amount and be 150ml, add S-WAT 0.65g as antioxidant, utilize the Ph=7.2 of 1.5mol/LLiOH regulator solution.Utilize 120 ℃ of lower heating 10h of oil bath (this laboratory use silicone oil), in heating, utilize mechanical stirrer (rotating speed=200 rev/min) to stir simultaneously, the solid of drag is carried out filtration washing 5 times, finally obtain presoma.
The water that filtration obtains and the mixing solutions of PBE are poured Rotary Evaporators into, and vacuum tightness is-0.09MPa, and when temperature reaches 70 ℃, water begins violent boiling and steams, and keeps temperature 6 hours, and moisture is separated fully.To not steam liquid filtering and remove precipitation and sl. sol. inorganic salt, the PBE that obtains utilizes refractometer to carry out purity test, makes the coprecipitation reaction of iron lithium phosphate in next time and reuses as organic solvent.
Presoma 20g and polyvinyl alcohol 3g be dissolved in spraying behind the 30g water obtain second particle, spraying machine is set spray parameters, 150 ℃ of inlet temperatures, and 65 ℃ of temperature outs obtain the iron lithium phosphate second particle.
Place tube furnace to carry out roasting second particle, pass into the mixed gas of 95% nitrogen and 5% hydrogen in tube furnace, be warmed up to 750 ℃ with the speed of 5 ℃/min, keep temperature 10h, stove naturally cools to room temperature, obtains the ball shape ferric phosphate lithium material.
LiFePO 4 material is carried out SEM detect, it is even that pattern can get the offspring particle diameter, and segmentation is few, and particle is spherical, can effectively increase tap density.
Claims (5)
1. a method for preparing the ferrous phosphate radical lithium salts is characterized in that, comprises the steps:
(1) preparation nano-scale lithium iron phosphate primary particle:
Take by weighing phosphoric acid salt, molysite, three kinds of raw materials of lithium salts, it is P: Fe: Li=1 according to molar ratio: 0.7～1.3: 2～4 ratio, be dissolved in water to 0.5～2mol/L, then lithium salts and phosphoric acid salt are mixed mutually, add again molysite after the formation precipitation to be mixed, after stirring 0.5-2h under the 200-600r/min, solution poured in the container heat, add simultaneously the high boiling organic solvent that accounts for mixed liquor volume 50%～80%, then the S-WAT that adds mixing solutions quality 0.5～2%, be that the pH value that 15%～40% ammoniacal liquor is regulated mixed reaction solution is 6.5～7.5 by adding 0.1～2mol/L lithium hydroxide or concentration again, Heating temperature remains on 100-120 ℃, then through 3～5 filtration washings, obtain lithium iron phosphate nano particle until flocks is formed on the bottom 1-5 hour heat-up time;
(2) spraying forms offspring:
The lithium iron phosphate nano particle that obtains is mixed according to mass ratio 1:1～1.5 with water, and the organic carbon source of adding iron lithium phosphate precursor mass ratio 10～30%, then use spray drying unit to spray, 130-180 ℃ of device inlet temperature, temperature out 50-100 ℃, obtain the iron lithium phosphate second particle;
(3) iron lithium phosphate sintering:
The iron lithium phosphate second particle that obtains is carried out sintering, in nitrogen atmosphere or nitrogen and the mixed atmosphere of hydrogen with volume ratio 1-5: 95-99, through 400-800 ℃ high-temperature roasting 6-25 hour then the cooling get final product.
2. a kind of method for preparing the ferrous phosphate radical lithium salts as claimed in claim 1 is characterized in that: utilize magnetic stirring apparatus to stir behind adding lithium salts and the phosphoric acid salt in the step (1) it is fully dissolved.
3. a kind of method for preparing the ferrous phosphate radical lithium salts as claimed in claim 1 is characterized in that: the employing of step (1) Raw lithium salts Quilonum Retard, lithium hydroxide or lithium fluoride; Molysite adopts Iron diacetate, Iron nitrate, iron protochloride or ferrous sulfate; Phosphoric acid salt adopts monometallic, primary ammonium phosphate, triammonium phosphate or phosphoric acid.
4. a kind of method for preparing the ferrous phosphate radical lithium salts as claimed in claim 1 is characterized in that: high boiling organic solvent employing methyl-sulphoxide, different fluorine that ketone or PBE in the step (1).
5. a kind of method for preparing the ferrous phosphate radical lithium salts as claimed in claim 1 is characterized in that: organic carbon source employing glucose, sucrose or polyvinyl alcohol in the step (2).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103400964A (en) * | 2013-07-23 | 2013-11-20 | 深圳市百纳新能源科技有限公司 | Preparation method of lithium iron phosphate electrode |
| CN103441255A (en) * | 2013-09-16 | 2013-12-11 | 宁德新能源科技有限公司 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN106876714A (en) * | 2017-01-23 | 2017-06-20 | 浙江钱江锂电科技有限公司 | A kind of lithium ion battery for automobile starting/stopping system |
| CN107565111A (en) * | 2017-08-28 | 2018-01-09 | 北方奥钛纳米技术有限公司 | The nano modification method of LiFePO4 and its nano modification LiFePO4 and lithium ion battery of preparation |
| CN108390061A (en) * | 2016-03-18 | 2018-08-10 | 王海峰 | A kind of LiFePO4 hydrothermal preparing process |
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| CN101567441A (en) * | 2009-06-09 | 2009-10-28 | 天津大学 | One-step preparation method of LiFePO4 powder coated with carbon |
| CN102303859A (en) * | 2011-07-20 | 2012-01-04 | 彩虹集团公司 | Preparation method of lithium iron phosphate material |
| CN102556998A (en) * | 2011-12-23 | 2012-07-11 | 彩虹集团公司 | Preparation method of lithium iron phosphate material |
-
2012
- 2012-10-15 CN CN2012103930323A patent/CN102910611A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101567441A (en) * | 2009-06-09 | 2009-10-28 | 天津大学 | One-step preparation method of LiFePO4 powder coated with carbon |
| CN102303859A (en) * | 2011-07-20 | 2012-01-04 | 彩虹集团公司 | Preparation method of lithium iron phosphate material |
| CN102556998A (en) * | 2011-12-23 | 2012-07-11 | 彩虹集团公司 | Preparation method of lithium iron phosphate material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103400964A (en) * | 2013-07-23 | 2013-11-20 | 深圳市百纳新能源科技有限公司 | Preparation method of lithium iron phosphate electrode |
| CN103400964B (en) * | 2013-07-23 | 2015-08-19 | 深圳市百纳新能源科技有限公司 | A kind of preparation method of iron phosphate lithium electrode |
| CN103441255A (en) * | 2013-09-16 | 2013-12-11 | 宁德新能源科技有限公司 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN103441255B (en) * | 2013-09-16 | 2017-02-01 | 宁德新能源科技有限公司 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN108390061A (en) * | 2016-03-18 | 2018-08-10 | 王海峰 | A kind of LiFePO4 hydrothermal preparing process |
| CN106876714A (en) * | 2017-01-23 | 2017-06-20 | 浙江钱江锂电科技有限公司 | A kind of lithium ion battery for automobile starting/stopping system |
| CN107565111A (en) * | 2017-08-28 | 2018-01-09 | 北方奥钛纳米技术有限公司 | The nano modification method of LiFePO4 and its nano modification LiFePO4 and lithium ion battery of preparation |
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Application publication date: 20130206 |