CN102227023A - Lithium iron phosphate precursor and preparing method thereof - Google Patents
Lithium iron phosphate precursor and preparing method thereof Download PDFInfo
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- CN102227023A CN102227023A CN2011101259912A CN201110125991A CN102227023A CN 102227023 A CN102227023 A CN 102227023A CN 2011101259912 A CN2011101259912 A CN 2011101259912A CN 201110125991 A CN201110125991 A CN 201110125991A CN 102227023 A CN102227023 A CN 102227023A
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Abstract
The invention discloses a method for preparing a lithium iron phosphate precursor by a liquid-phase composite crystal method, comprising the following steps: reacting an iron compound, a lithium compound, a phosphorus compound, a doped chemical compound, organic negative ions and a dispersing agent in a solvent at a mole ratio to form a lithium iron phosphate precursor liquid of an organic composite crystal; and filtering, centrifuging or drying the precursor liquid to obtain the lithium iron phosphate precursor of a (Li<+>Fe<3+.PO4<3->)<+>nR<n->organic composite crystal. The method can be used to solve the problems that the material performances are unstable, the cycle life is short, the batch stability is poor due to the residual Fe<3+> because carbon can not be combined with Fe<3+> uniformly to carry out carbothermic reduction in a ferric iron productive technology, thus elements in the lithium iron phosphate precursor are mixed evenly in an atom level, thereby improving the performances and the batch stability of lithium iron phosphate products greatly.
Description
Technical field
The present patent application relates to a kind of ferric lithium phosphate precursor and preparation method thereof, belongs to the anode material for lithium-ion batteries field.
Background technology
Along with fast development of society, the continuous progress of science and technology, more and more higher to the requirement of fail safe, the feature of environmental protection and the practicality aspect of the energy, and these development with lithium ion battery are inseparable.
Since Sony in 1991 takes the lead in Li
xC
6/ Li
1-xCoO
2Since the lithium ion battery commercialization, lithium ion battery is widely used.Wherein commercial positive electrode LiCoO
2Because cobalt resource scarcity, contaminated environment, and it overcharges insecurity, has determined it not to be applied in high capacity cell.LiNi
0.3Co
0.3Mn
0.3O
2Can not promote LiMnO owing to the restriction of cobalt resource equally
4Property that structure is understable, discharge capacity is relatively low, is subjected to the influence of factors such as decomposition of dissolving, the electrolyte of manganese, makes it that capacity attenuation take place in cyclic process easily.LiNiO
2Synthetic difficulty, cycle performance is poor, though it has been carried out modification, the possibility of practical application is little.
The LiFePO4 electrode material is mainly used in various lithium ion batteries, discloses AyMPO first from the NTT of Japan in 1996
4(A is an alkali metal, and M is both combinations of Co Fe: LiFeCOPO
4) the anode material of lithium battery of olivine structural after, LiFePO group has also then been reported in researchs such as the upright John.B.Goodenough of university of Texas, USA in 1997
4Invertibity the characteristic of the lithium of moving into, the U.S. and Japan coincidentally deliver the LiMPO of olivine structural
4, make this material be subjected to great attention, and cause extensive studies and development rapidly.With traditional lithium ion secondary battery anode material, the LiMn of spinel structure
2O
4LiCoO with layer structure
2Compare LiMPO
4Former material source more extensive, price is cheaper and non-environmental-pollution.
LiFePO4 is a kind of new type lithium ion battery electrode material, is characterized in that discharge capacity is big, and is cheap, and avirulence does not cause environmental pollution.But LiFePO4 has three major defects as positive electrode: 1. low electron conductivity; 2. low bulk density; 3. low lithium ion diffusion coefficient.Along with deepening continuously that LiFePO4 is studied, the problem of material itself solves step by step, and key is how can stably three kinds of method of modifying should be made good use of on producing.
Now a lot of production technologies can both be in lab scale better performances, but after producing amplification a lot of problems will appear, wherein reason is ferric lithium phosphate precursor preparation technology instability to a great extent: 1. produce the process that goes up the preparation presoma and mainly adopt ball-milling technology, ball milling batch unsettled situation appears easily after producing amplification, abrading-ball and spherical tank contaminated feedstock, and can't realize when carrying out metal ion mixing fully evenly; 2. owing to adopt solid particle as presoma, not only will consider the purity of raw material, the granule size of raw material, particle size distribution, reunion situation all can exert an influence to end properties, and batch stability of raw material has a significant impact finished product.
Summary of the invention
The present patent application promptly be at present in anode material for lithium-ion batteries field above shortcomings part, a kind of ferric lithium phosphate precursor and preparation method thereof is provided.
One of purpose of the present patent application provides a kind of ferric lithium phosphate precursor.
Specifically, the described ferric lithium phosphate precursor of the present patent application is to adopt liquid phase composite crystal method prepared, and its molecular structure is (Li
+Fe
3+PO
4 3-)
+ nR
N-, wherein, R
N-For long carbochain organic anion, with Li
+, Fe
3+, PO
4 3-Form organic composite crystal.
Above-mentioned ferric lithium phosphate precursor is at organic composite crystal (Li
+Fe
3+PO
4 3-)
+ nR
N-In, according to the chemical valence of long carbochain organic anion, n=1,2,3,4 or 5.
Another purpose of the present patent application provides the preparation method of above-mentioned ferric lithium phosphate precursor.
The preparation method of described ferric lithium phosphate precursor comprises following step:
The preparation method of the described ferric lithium phosphate precursor of claim 1 is characterized in that: comprise following step:
1, iron compound, lithium compound, phosphorus compound, doping element compound, organic anion, dispersant are pressed certain mol proportion and in solvent, reacted formation composite crystal LiFePO4 precursor liquid;
2, composite crystal LiFePO4 precursor liquid is filtered, centrifugal or dry 3-10 hour, obtain organic composite crystal ferric lithium phosphate precursor;
3, again presoma is placed the sintering furnace of inert gas shielding, in 450-700 ℃ temperature range sintering 4-15 hour, obtain lithium iron phosphate positive material.
In above-mentioned preparation method, the filter membrane aperture of filtration is between 0.05 to 500 μ m; Centrifugal rotation speed is 1000 to 15000rpm; Dry method can be used one or more the combination in constant pressure and dry, vacuumize, spray drying, the fluidized bed drying; Baking temperature is in 60-350 ℃ temperature range.
In above-mentioned preparation method, described lithium compound comprises one or more the combination in lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate, lithium chloride, platinic acid lithium, lithium vanadate, lithium nitrite, lithium dihydrogen phosphate, lithium phosphate, lithium acetate, lithium fluoride, lithium iodide, the lithia.
In above-mentioned preparation method, described iron compound comprises one or more the combination in iron chloride, ferric nitrate, ironic citrate, ferric acetate, ferric tannate, ferric oxalate and the bodied ferric sulfate.
In above-mentioned preparation method, described phosphorus compound comprises one or more the combination in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the lithium dihydrogen phosphate.
In above-mentioned preparation method, described doping metals compound comprises one or more the combination in nickel salt or its oxide, mantoquita or its oxide, actinium salt or its oxide, lanthanum salt or its oxide, manganese salt or its oxide, cobalt salt or its oxide, magnesium salts or its oxide, aluminium salt or its oxide, titanium salt or its oxide, zinc salt or its oxide, barium salt or its oxide, vanadic salts or its oxide, chromic salts or its oxide, niobium salt or its oxide.
In above-mentioned preparation method, described organic anion is an organic complexing agent, comprises one or more the combination in glucose acid group anion, lactic acid anion, malonate anion, ethanedioic acid root anion, citrate anion, ascorbic acid root anion, the malate anion.
In above-mentioned preparation method, described dispersant comprises one or more the combination in stearmide, atoleine, polyethylene glycol, polyacrylamide, hexadecyltrimethylammonium chloride, the softex kw.
In above-mentioned preparation method, described solvent comprises one or more the combination in absolute ethyl alcohol, acetone, acetate, the water.
In above-mentioned preparation method, the mol ratio of described initial action compound is according in lithium compound, iron compound, phosphorus compound, doping element compound, organic anion and the dispersant, lithium ion: iron ion: phosphate anion: doped chemical: organic anion: dispersant=X: Y: Z: K: M: N, reactant molar ratio x wherein, y, z, k, m, the scope of the numerical value of n is respectively: 0.90≤x≤1.10,0.70≤y≤1.20,0.90≤z≤1.20,0.01≤k≤0.30,0.20≤m≤3.00,0.01≤n≤1.00.
The present invention has following advantage:
With existing production process in the ferric iron Fe that extensively adopts
2O
3With FePO
4Compare Fe as raw material
3+With R
N-The even contact combination, in the process of carbon thermal reduction, all Fe
3+All can be by R
N-Be reduced into Fe
2+, and still have unnecessary carbon residue original position to be coated on single-crystal surface, reduce grain size to greatest extent, reach nanoscale, thereby improve conductivity, can solve in the existing ferric iron production technology carbon can't be equably and Fe
3+In conjunction with carrying out carbon thermal reduction, residual Fe
3+Cause problems such as material property instability, cycle life weak point, batch poor stability;
2. various elements mix on atomic level in presoma, make presoma keep homogeneity, and batch stability of finished product is improved greatly;
3. need not adopt ball-milling technology to carry out the mixing of raw material, but in liquid-phase system, form uniform presoma naturally, make metal ion mixing can on atomic level, reach even, little test result and production are consistent, also make and produce the dependence of having broken away from feedstock particle size and particle size uniformity, more reduce production cost, simplified production procedure, shortened the production cycle;
4. because source of iron, lithium source and phosphorus source can evenly distribute on molecular level, can reduce sintering time and temperature, thereby reduce production cost.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the ferric lithium phosphate precursor of the present patent application embodiment preparation;
Fig. 2 is the X ray diffracting spectrum of the LiFePO4 of the present patent application embodiment preparation;
Fig. 3 is the SEM figure of the LiFePO4 of the present patent application embodiment preparation;
Fig. 4 is the discharge curve of 1C of the LiFePO4 of the present patent application embodiment preparation;
Fig. 5 is the cyclic curve figure of 1C of the LiFePO4 of the present patent application embodiment preparation.
Embodiment
Below in conjunction with concrete execution mode; described ferric lithium phosphate precursor of the present patent application and preparation method thereof is described; purpose is better to understand the described technology contents of the present patent application for the public; rather than to the restriction of described technology contents; in fact; the improvement of described ferric lithium phosphate precursor of the present patent application and preparation method thereof being carried out in the principle identical or approximate with the present patent application; all be that persons skilled in the art need not performing creative labour and can obtain, therefore all within the present patent application technical scheme required for protection.
Embodiment 1
With ferric acetate 0.9mol; ascorbic acid 0.5mol is water-soluble; with lithium carbonate 0.5mol; phosphatase 11 mol is water-soluble; with ascorbic acid and ferric acetate solution vigorous stirring; slowly add lithium carbonate and phosphoric acid solution; dropwise add absolute ethyl alcohol; the nano titanium oxide 0.1mol that adds ultrasonic dispersion again; the last dispersant hexadecyltrimethylammonium chloride 0.1mol that slowly adds; stir 1 hour afterreaction and form organic composite crystal LiFePO4 precursor liquid; place vacuum drying chamber vacuumize drying in 80 to 105 ℃ temperature range to obtain organic composite crystal ferric lithium phosphate precursor in 3 to 10 hours precursor liquid; the sintering furnace that the gained presoma is placed nitrogen protection to 8h, obtains the nano-grade lithium iron phosphate powder body material at 500 to 600 ℃ temperature sintering 4.
Observing the product pattern through field emission scanning electron microscope is olivine structural, and particle diameter is 80-100nm, and detecting with the X-ray powder diffraction is LiFePO
4
LiFePO4, PVDF and the acetylene black of preparation by 88: 4: 8 mixed, is added and stirs 10h behind the NMP and make slurry.With scraper slurry evenly is applied on the aluminium foil, at 120 ℃ of following vacuumize 3h, as positive pole.As negative pole, adopt the TC-E808 electrolyte of Guangzhou Tianci Advanced Materials Co., Ltd with the lithium sheet, make the CR2032 button cell, battery is carried out the charge-discharge performance test.Adopt the mode of constant current charge to charge, the charging stopping potential is 4.2V, adopts constant-current discharge, cut-ff voltage is 2.5V, and charging and discharging currents is 1C, and first discharge specific capacity is 144mAh/g, for the second time specific discharge capacity is 150mAh/g, and circulating, specific discharge capacity is 146mAh/g after 400 times.
Embodiment 2
With iron chloride 0.95mol; magnesium acetate 0.05mol; citric acid 0.33mol is dissolved in ethanol; slowly add lithium dihydrogen phosphate 1mol in the vigorous stirring; the last dispersant polyethylene glycol 5g that slowly adds; stir 2 hours afterreactions and form composite crystal LiFePO4 precursor liquid; place vacuum drying chamber to obtain organic composite crystal ferric lithium phosphate precursor in 3 to 5 hours sediment by the centrifuge of 5000rpm after centrifugal precursor liquid at 60 to 80 ℃ temperature drying; the sintering furnace that the gained presoma is placed argon shield to 15h, obtains the nano-grade lithium iron phosphate powder body material at 500 to 550 ℃ temperature sintering 8.
Observing the product pattern through field emission scanning electron microscope is olivine structural, and particle diameter is 100-150nm, and detecting with the X-ray powder diffraction is LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1, and first discharge specific capacity is 142mAh/g, and for the second time specific discharge capacity is 146mAh/g, and circulating, specific discharge capacity is 140mAh/g after 400 times.
Embodiment 3
With ferric nitrate 0.95mol; manganese acetate 0.05mol; ethanedioic acid 0.5mol is water-soluble; slowly add ammonium dihydrogen phosphate and lithium nitrate 1mol in the vigorous stirring; the last dispersant polyethylene glycol 10g that slowly adds; stir 4 hours afterreactions and form composite crystal LiFePO4 precursor liquid; place a conventional oven to obtain organic composite crystal ferric lithium phosphate precursor in 4 to 6 hours sediment after by the filter membrane of 1 μ m precursor liquid at 120 to 150 ℃ temperature drying; the sintering furnace that the gained presoma is placed argon shield to 10h, obtains the nano-grade lithium iron phosphate powder body material at 600 to 680 ℃ temperature sintering 5.
Observing the product pattern through field emission scanning electron microscope is olivine structural, and particle diameter is 100-200nm, and detecting with the X-ray powder diffraction is LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1, and first discharge specific capacity is 138mAh/g, and for the second time specific discharge capacity is 144mAh/g, and circulating, specific discharge capacity is 135mAh/g after 400 times.
Embodiment 4
With ironic citrate 0.9mol; cobalt acetate 0.05mol; magnesium acetate 0.05mol; be dissolved in the acetic acid solution; slowly add ammonium dihydrogen phosphate and each 1mol of lithium nitrate solution in the vigorous stirring; the last dispersant liq paraffin 5ml that slowly adds; stir 3 hours afterreactions and form composite crystal LiFePO4 precursor liquid; place a conventional oven to obtain organic composite crystal ferric lithium phosphate precursor in 4 to 6 hours sediment by the centrifuge of 5000rpm after centrifugal precursor liquid at 120 to 150 ℃ temperature drying; the sintering furnace that the gained presoma is placed argon shield to 8h, obtains the nano-grade lithium iron phosphate powder body material at 500 to 650 ℃ temperature sintering 4.
Observing the product pattern through field emission scanning electron microscope is olivine structural, and particle diameter is 100-200nm, and detecting with the X-ray powder diffraction is LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1, and first discharge specific capacity is 138mAh/g, and for the second time specific discharge capacity is 141mAh/g, and circulating, specific discharge capacity is 133mAh/g after 400 times.
Embodiment 5
With ferric oxalate 0.91mol; manganese acetate 0.03mol; magnesium acetate 0.03mol; citric acid 0.33mol is water-soluble; slowly add vanadic oxide 0.015mol in the vigorous stirring; lithium dihydrogen phosphate 1mol; the last dispersant polyethylene glycol 15g that slowly adds; stir 2 hours afterreactions and form composite crystal LiFePO4 precursor liquid; precursor liquid spray drying under 250 to 350 ℃ temperature is obtained organic composite crystal ferric lithium phosphate precursor; the sintering furnace that the gained presoma is placed argon shield to 15h, obtains the nano-grade lithium iron phosphate powder body material at 500 to 650 ℃ temperature sintering 8.
Observing the product pattern through field emission scanning electron microscope is olivine structural, and particle diameter is 80-150nm, and detecting with the X-ray powder diffraction is LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1, and first discharge specific capacity is 144mAh/g, and for the second time specific discharge capacity is 148mAh/g, and circulating, specific discharge capacity is 142mAh/g after 400 times.
Embodiment 6
With ironic citrate 0.95mol; lanthanum acetate 0.02mol; ethanedioic acid 1mol is water-soluble; slowly add vanadic oxide 0.015mol in the vigorous stirring; mix with ironic citrate solution after in 1mol phosphoric acid, dissolving in lithium carbonate 1mol; the last dispersant softex kw 0.1mol that slowly adds; stir 1 hour afterreaction and form composite crystal LiFePO4 precursor liquid; precursor liquid spray drying under 250 to 350 ℃ temperature is obtained organic composite crystal ferric lithium phosphate precursor; the sintering furnace that the gained presoma is placed argon shield to 15h, obtains the nano-grade lithium iron phosphate powder body material at 500 to 650 ℃ temperature sintering 8.
Observing the product pattern through field emission scanning electron microscope is olivine structural, and particle diameter is 80-150nm, and detecting with the X-ray powder diffraction is LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1, and first discharge specific capacity is 140mAh/g, and for the second time specific discharge capacity is 142mAh/g, and circulating, specific discharge capacity is 135mAh/g after 400 times.
Embodiment 7
With ferric oxalate 1mol; citric acid 0.33mol is water-soluble; slowly add lithium dihydrogen phosphate 1mol in the vigorous stirring; the last dispersant polyacrylamide 15g that slowly adds; stir 2 hours afterreactions and form composite crystal LiFePO4 precursor liquid; with precursor liquid in 120 to 150 ℃ vacuum drying chamber dry 3 to 5h; obtain organic composite crystal ferric lithium phosphate precursor; the sintering furnace that the gained presoma is placed nitrogen protection to 15h, obtains the nano-grade lithium iron phosphate powder body material at 450 to 650 ℃ temperature sintering 8.
Observing the product pattern through field emission scanning electron microscope is olivine structural, and particle diameter is 100-150nm, and detecting with the X-ray powder diffraction is LiFePO
4
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1, and first discharge specific capacity is 134mAh/g, and for the second time specific discharge capacity is 137mAh/g, and circulating, specific discharge capacity is 128mAh/g after 400 times.
Claims (10)
1. ferric lithium phosphate precursor, it is characterized in that: described ferric lithium phosphate precursor, its molecular structure are (Li
+Fe
3+PO
4 3-)
+ nR
N-, wherein, R
N-For long carbochain organic anion, with Li
+, Fe
3+And PO
4 3-Form organic composite crystal.
2. ferric lithium phosphate precursor according to claim 1 is characterized in that: at organic composite crystal (Li
+Fe
3+PO
4 3-)
+ nR
N-In, n=1,2,3,4 or 5.
3. the preparation method of the described ferric lithium phosphate precursor of claim 1, it is characterized in that: described preparation method comprises following step:
1) iron compound, lithium compound, phosphorus compound, doping element compound, organic anion, dispersant are pressed certain mol proportion and in solvent, reacted formation composite crystal LiFePO4 precursor liquid;
2) composite crystal LiFePO4 precursor liquid is filtered, centrifugal or dry 3-10 hour, obtain organic composite crystal ferric lithium phosphate precursor;
3) again presoma is placed the sintering furnace of inert gas shielding, in 450-700 ℃ temperature range sintering 4-15 hour, obtain lithium iron phosphate positive material.
4. preparation method according to claim 3 is characterized in that: the filter membrane aperture of filtration is between 0.05 to 500 μ m; Centrifugal rotation speed is 1000 to 15000rpm; Dry method can be used one or more the combination in constant pressure and dry, vacuumize, spray drying, the fluidized bed drying, and baking temperature is in 60-350 ℃ temperature range.
5. preparation method according to claim 3 is characterized in that: described lithium compound comprises one or more the combination in lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate, lithium chloride, platinic acid lithium, lithium vanadate, lithium nitrite, lithium dihydrogen phosphate, lithium phosphate, lithium acetate, lithium fluoride, lithium iodide, the lithia; Described iron compound comprises one or more the combination in iron chloride, ferric nitrate, ironic citrate, ferric acetate, ferric tannate, ferric oxalate and the bodied ferric sulfate; Described phosphorus compound comprises one or more the combination in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the lithium dihydrogen phosphate.
6. preparation method according to claim 3 is characterized in that: described doping metals compound comprises one or more the combination in nickel salt or its oxide, mantoquita or its oxide, actinium salt or its oxide, lanthanum salt or its oxide, manganese salt or its oxide, cobalt salt or its oxide, magnesium salts or its oxide, aluminium salt or its oxide, titanium salt or its oxide, zinc salt or its oxide, barium salt or its oxide, vanadic salts or its oxide, chromic salts or its oxide, girl's salt or its oxide.
7. preparation method according to claim 3 is characterized in that: described organic anion comprises one or more the combination in glucose acid group anion, lactic acid anion, malonate anion, ethanedioic acid root anion, citrate anion, ascorbic acid root anion, the malate anion.
8. preparation method according to claim 3 is characterized in that: described dispersant comprises one or more the combination in stearmide, atoleine, polyethylene glycol, polyacrylamide, hexadecyltrimethylammonium chloride, the softex kw.
9. preparation method according to claim 3 is characterized in that: described solvent comprises one or more the combination in absolute ethyl alcohol, acetone, acetate, the water.
10. preparation method according to claim 3, it is characterized in that: the mol ratio of described initial action compound is according to lithium compound, iron compound, phosphorus compound, doping element compound, in organic anion and the dispersant, lithium ion: iron ion: phosphate anion: doped chemical: organic anion: dispersant=X: Y: Z: K: M: N, reactant molar ratio x wherein, y, z, k, m, the scope of the numerical value of n is respectively: 0.90≤x≤1.10,0.70≤y≤1.20,0.90≤z≤1.20,0.01≤k≤0.30,0.20≤m≤3.00,0.01≤n≤1.00.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474654A (en) * | 2012-06-05 | 2013-12-25 | 喻维杰 | Preparation method of nanometer ultrafine lithium iron phosphate material |
| CN105449237A (en) * | 2015-11-25 | 2016-03-30 | 四川长虹新能源科技股份有限公司 | Alkaline dry battery |
| CN108091833A (en) * | 2017-11-14 | 2018-05-29 | 山东丰元化学股份有限公司 | A kind of high compacted density composite ferric lithium phosphate material and preparation method thereof |
| CN113860281A (en) * | 2021-09-26 | 2021-12-31 | 桂林理工大学 | Method for preparing lithium iron phosphate as positive electrode material of lithium ion battery by using polymeric ferric sulfate as iron source |
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| CN101993054A (en) * | 2010-11-17 | 2011-03-30 | 河北师范大学 | Method for preparing lithium ion phosphate material |
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| WO2009003093A1 (en) * | 2007-06-26 | 2008-12-31 | Tiax, Llc | Metal phosphate compounds and batteries containing the same |
| CN101172599A (en) * | 2007-11-12 | 2008-05-07 | 杭州电子科技大学 | Process for producing carbon coated iron lithium phosphate |
| CN101794880A (en) * | 2007-11-14 | 2010-08-04 | 中国科学院理化技术研究所 | Preparation method of positive-electrode cellular material used by lithium ion battery |
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| CN103474654A (en) * | 2012-06-05 | 2013-12-25 | 喻维杰 | Preparation method of nanometer ultrafine lithium iron phosphate material |
| CN105449237A (en) * | 2015-11-25 | 2016-03-30 | 四川长虹新能源科技股份有限公司 | Alkaline dry battery |
| CN108091833A (en) * | 2017-11-14 | 2018-05-29 | 山东丰元化学股份有限公司 | A kind of high compacted density composite ferric lithium phosphate material and preparation method thereof |
| CN113860281A (en) * | 2021-09-26 | 2021-12-31 | 桂林理工大学 | Method for preparing lithium iron phosphate as positive electrode material of lithium ion battery by using polymeric ferric sulfate as iron source |
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Application publication date: 20111026 |