CN1299369C - Method for preparing high-density spherical lithium iron phosphate - Google Patents
Method for preparing high-density spherical lithium iron phosphate Download PDFInfo
- Publication number
- CN1299369C CN1299369C CNB2005100001679A CN200510000167A CN1299369C CN 1299369 C CN1299369 C CN 1299369C CN B2005100001679 A CNB2005100001679 A CN B2005100001679A CN 200510000167 A CN200510000167 A CN 200510000167A CN 1299369 C CN1299369 C CN 1299369C
- Authority
- CN
- China
- Prior art keywords
- spherical
- lithium
- solution
- aqueous solution
- iron phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a method for preparing high-density spherical lithium iron phosphate, which belongs to the technical field of the preparation of energy materials. The method for preparing high-density spherical lithium iron phosphate comprises the following steps: iron nitrate, phosphoric acid and acetic acid lithium are used as raw materials, and the raw materials are dissolved by adding water without ion to prepare solution A, or an impurity mixed metal compound or a carbon source is added in the solution A; hexamethylenetetramine and carbamide are dissolved by adding water to prepare solution B; new mixed water solution C is prepared by adding the B in the A, the solution C is dropped in kerosene, the mixture of the solution C and the kerosene is heated and changed into sol, the sol is converted into gel and is deposited out, and a spherical dry gel precursor is obtained after centrifugal separation; the spherical lithium iron phosphate with high volume ratio capacity and high density is obtained by a heat treatment with high temperature, the average particle diameter of the lithium iron phosphate is from 5 to 8 mu m, the tap density of the lithium iron phosphate can reach 1.8 to 2.0 g/cm<3>, and under room temperature, the first discharge ratio capacity of the lithium iron phosphate can reach from 140 to 160 mAh/g. The method for preparing high-density spherical lithium iron phosphate has simple manufacturing process and large application value and can easily mix metal ions and carbon to enhance the electric conductivity of the lithium iron phosphate.
Description
Technical field
The invention belongs to the energy and material technical field.Be particularly related to preparation method as a kind of high-density spherical ferric lithium phosphate of anode material for lithium-ion batteries.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, numerous advantages such as have that voltage height, energy density are big, good cycle, self discharge are little, memory-less effect, operating temperature range are wide, be widely used in mobile phone, notebook computer, UPS, video camera, various portable power tool, electronic instrument, weaponry etc., in electric automobile, also have a good application prospect, be considered to be in 21st century national economy and the significant new high-tech product of people's lives.
Positive electrode is the important component part of lithium ion battery.At present, the maximum positive electrode of research is LiCoO
2, LiNiO
2, LiMn
2O
4LiCoO
2Be the positive electrode of unique large-scale commercial, the research comparative maturity, high comprehensive performance, but cost an arm and a leg, capacity is lower, and toxicity is bigger, has certain safety issue, and expectation will be replaced by the new material of high-performance and low-cost.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, there are comparatively serious safety problem in the consistency of material property and poor reproducibility.Spinelle LiMn
2O
4Cost is low, and fail safe is good, but cycle performance especially high temperature cyclic performance is poor, certain dissolubility is arranged in electrolyte, storge quality is poor.The research and development novel anode material becomes current focus.
LiFePO4 (the LiFePO of quadrature olivine structural
4) positive electrode becomes new research focus both at home and abroad gradually.Primary Study shows that this novel anode material has been concentrated LiCoO
2, LiNiO
2, LiMn
2O
4Advantage separately Deng material: do not contain noble element, raw material cheapness, resource are greatly abundant; Operating voltage moderate (3.4V); Platform identity is good, and voltage pole is (can match in excellence or beauty with stabilized voltage power supply) steadily; Theoretical capacity big (170mAh/g); Stability Analysis of Structures, security performance splendid (O and P make material be difficult to analyse oxygen and decompose with the strong covalent bond strong bonded); High-temperature behavior and good cycle; Volume-diminished during charging, the bulk effect when cooperating with carbon negative pole material is good; Good with most of electrolyte system compatibilities, storge quality is good; Nontoxic, be real green material.
Yet there are two significant disadvantages in LiFePO4, the one, and conductivity is low, causes high-rate charge-discharge capability poor, and actual specific capacity is low; The 2nd, bulk density is low, causes volume and capacity ratio low.These two shortcomings have hindered the practical application of this material.
At present, synthesizing iron lithium phosphate is about to lithium source, phosphorus source, source of iron ground and mixed together mainly by high-temperature solid phase reaction method, and at high temperature calcining is synthetic.In the ground and mixed process, mix foreign metal compound or carbon source, improve the conductivity of material.There is significant disadvantages in this method, and the one, foreign metal compound that mixes or carbon source are failed with lithium source, phosphorus source, source of iron is full and uniform mixes, and fails to reach the effect of abundant doping, and the conductivity of material is improved not obvious.The 2nd, the powder body material that synthesizes is made up of random particle, and bulk density is low, and general tap density only is 1.0g/cm
3, than cobalt acid lithium (general tap density 2.2-2.5g/cm
3, the high 2.8-2.9g/cm that reaches
3) much lower, low bulk density makes that the volume and capacity ratio of LiFePO4 is more much lower than the sour lithium of cobalt, has no advantage and can say, has hindered the practical application of this material.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of high-density spherical ferric lithium phosphate.It is characterized in that: the technology of described preparation spherical LiFePO 4 is to improve the tap density and the volume and capacity ratio of material by the spheroidization of LiFePO4 particle, and by doped metal ion or carbon dope, improves the conductivity of material.
The technology of the spherical LiFePO 4 of described preparation spherical LiFePO 4 or doping metal ion or the spherical LiFePO 4 of carbon dope comprises following each step:
1) takes by weighing ferric nitrate, phosphoric acid, lithium acetate at 1: 1: 1 with mol ratio, be dissolved in deionized water, make the mixed aqueous solution A that three kinds of concentration of aqueous solution are ferric nitrate, phosphoric acid and the lithium acetate of 1～3mol/L; Or in mixed aqueous solution A, mix doping metals compound or doping carbon source again;
2) be (1～5) by mass ratio: 1 takes by weighing urea and hexamethylenetetramine, adds deionized water and makes its dissolving, and making concentration is the aqueous solution B of 200～400g/L;
3) in 5 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A solution, make mixed aqueous solution C;
4) be dispersant with kerosene, press mass ratio and in kerosene, add the span80 of 0.1%-5% as surfactant; With the 3rd) the mixed aqueous solution C that makes of step slowly is added dropwise in the dispersant volume ratio 1 of solution C and dispersant kerosene: (5～20) under stirring condition; Be warming up to 70～80 ℃ after being added dropwise to complete, be incubated and stop heating after 10～20 minutes and stir, make mixed aqueous solution change colloidal sol into, and then change into gel precipitation and come out;
5) centrifugation of step 4) gained gel is obtained spherical xerogel presoma;
6) with the spherical xerogel presoma of step 5) gained flow be the 0.1-10 liter/minute 90% nitrogen+10% hydrogen mixed gas protected down, obtained the spherical LiFePO 4 of spherical LiFePO 4 or doping metal ion or the spherical LiFePO 4 of carbon dope in high-temperature heat treatment 8-48 hour through 600-900 ℃.
In step 1), the doping metals compound that mixes is one or more in magnesium nitrate, aluminum nitrate, titanium tetrachloride, zirconium oxychloride or the ammonium niobium oxalate, and consumption is doping metals compound/lithium=0.5%～2% in molar ratio.
In step 1), the doping carbon source of mixing is one or more in sucrose or the glucose, and consumption is sucrose or glucose/LiFePO4=0.5wt%～15wt%.
The invention has the beneficial effects as follows: it is 5-8 μ m that this preparation method prepares average grain diameter, and tap density can reach 1.8-2.0g/cm
3, first discharge specific capacity can reach the high-bulk-density of 140-160mAh/g, the lithium ion battery anode material spherical LiFePO 4 of high-volume and capacity ratio under the room temperature.The technological process of the preparation spherical LiFePO 4 that the present invention set up is simple, is easy to realize even doping metal ion and carbon, to improve the conductivity of product, has very big using value.
Embodiment
The present invention proposes a kind of preparation method of high-density spherical ferric lithium phosphate, improves the tap density and the volume and capacity ratio of material by the spheroidization of LiFePO4 particle, and by doped metal ion or carbon dope, improves the conductivity of material.
The technology of the spherical LiFePO 4 of designed preparation spherical LiFePO 4 or the spherical LiFePO 4 of doping metal ion or carbon dope comprises following each step:
1) takes by weighing certain amount of ferric nitrate, phosphoric acid, lithium acetate at 1: 1: 1 with mol ratio, be dissolved in deionized water, make ferric nitrate, phosphoric acid and lithium acetate mixed aqueous solution A that three kinds of concentration of aqueous solution are 1～3mol/L; Or in aforementioned ferric nitrate, phosphoric acid and lithium acetate mixed aqueous solution, mix a small amount of doping metals compound again, make ferric nitrate, phosphoric acid, lithium acetate, doping metals compound water solution A; Or in aforementioned ferric nitrate, phosphoric acid and lithium acetate mixed aqueous solution, mix a small amount of doping carbon source again, make ferric nitrate, phosphoric acid, lithium acetate, doping carbon source mixed aqueous solution A;
2) be (1～5) by mass ratio: 1 takes by weighing urea and hexamethylenetetramine, adds deionized water and makes its dissolving, and making concentration is the aqueous solution B of 200～400g/L;
3) in 5 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A solution, make mixed aqueous solution C;
4) be dispersant with kerosene, press mass ratio and in kerosene, add the span80 of 0.1%-5% as surfactant; With the 3rd) the mixed aqueous solution C that makes of step slowly is added dropwise in the dispersant volume ratio 1 of solution C and dispersant kerosene: (5～20) under stirring condition; Be warming up to 70～80 ℃ after being added dropwise to complete, be incubated and stop heating after 10～20 minutes and stir, make mixed aqueous solution change colloidal sol into, and then change into gel precipitation and come out;
5) centrifugation of step 4) gained gel is obtained spherical xerogel presoma;
6) with the spherical xerogel presoma of step 5) gained flow be the 0.1-10 liter/minute 90% nitrogen+10% hydrogen mixed gas protected down, obtained the spherical LiFePO 4 of spherical LiFePO 4 or doping metal ion or the spherical LiFePO 4 of carbon dope in high-temperature heat treatment 8-48 hour through 600-900 ℃.
In step 1), described doping metals compound is one or more in magnesium nitrate, aluminum nitrate, titanium tetrachloride, zirconium oxychloride or the ammonium niobium oxalate, and consumption is doping metals compound/lithium=0.5%～2% in molar ratio.
In step 1), described doping carbon source is one or more in sucrose or the glucose, and consumption is sucrose or glucose/LiFePO4=0.5wt%～15wt%.
Introduce embodiments of the invention below:
Embodiment 1
Measure about 20ml deionized water, insert in the beaker, take by weighing 20.2g ferric nitrate (Fe (NO
3)
39H
2O), 4.9g phosphoric acid (H
3PO
4), 5.1g lithium acetate (CH
3COOLi2H
2O), be dissolved in the deionized water, make the mixed aqueous solution A that ferric nitrate, phosphoric acid, lithium acetate concentration are 2.5mol/L.Take by weighing hexamethylenetetramine (methenamine) 4.5g and urea 9g more respectively, insert in another beaker, add about 20ml deionized water dissolve solution B.Under temperature is 10 ℃ and stirring condition, the B drips of solution is added in the A solution, make new mixed aqueous solution C.With kerosene is dispersant, presses mass ratio and adds 3% span80 as surfactant in kerosene, the mixed aqueous solution C that newly makes slowly is added dropwise in the dispersant volume ratio of solution C and dispersant kerosene 1: 10 under stirring condition.Be warming up to 70 ℃ after being added dropwise to complete, be incubated and stop heating after 10 minutes and stir gel precipitation is come out.Centrifugation obtains spherical xerogel presoma.The xerogel presoma is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains the spherical LiFePO 4 product.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.90g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 140mAh/g.
Embodiment 2
Measure about 20ml deionized water, insert in the beaker, take by weighing 8.08g ferric nitrate (Fe (NO
3)
39H
2O), 1.96g phosphoric acid (H
3PO
4), 2.04g lithium acetate (CH
3COOLi2H
2O) be dissolved in the deionized water, make the mixed aqueous solution A that ferric nitrate, phosphoric acid, lithium acetate concentration are 1mol/L.Take by weighing hexamethylenetetramine (methenamine) more respectively and each 4.5g of urea inserts in another beaker, add about 20ml deionized water dissolve solution B.Under temperature is 5 ℃ and stirring condition, the B drips of solution is added in the A solution, make new mixed aqueous solution C.With kerosene is dispersant, presses mass ratio and adds 1% span80 as surfactant in kerosene, the mixed aqueous solution C that newly makes slowly is added dropwise in the dispersant volume ratio of solution C and dispersant kerosene 1: 15 under stirring condition.Be warming up to 75 ℃ after being added dropwise to complete, be incubated and stop heating after 10 minutes and stir gel precipitation is come out.Centrifugation obtains spherical xerogel presoma.The xerogel presoma is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains the spherical LiFePO 4 product.Recording this product average grain diameter is 5-7 μ m, and tap density is 1.85g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 140mAh/g.
Embodiment 3
Measure about 20ml deionized water, insert in the beaker, take by weighing 20.2g ferric nitrate (Fe (NO
3)
39H
2O), 4.9g phosphoric acid (H
3PO
4), 5.1g lithium acetate (CH
3COOLi2H
2O), the 0.1875g ammonium niobium oxalate is dissolved in the deionized water, makes ferric nitrate, phosphoric acid, lithium acetate concentration and is 2.5mol/L, ammonium niobium oxalate concentration is the mixed aqueous solution A (niobium/lithium=0.01, mol ratio) of 0.025mol/L.Take by weighing hexamethylenetetramine (methenamine) 4.5g and urea 9g more respectively, insert in another beaker, add about 20ml deionized water dissolve solution B.Under temperature is 10 ℃ and stirring condition, the B drips of solution is added in the A solution, make new mixed aqueous solution C.With kerosene is dispersant, add 3% span80 more therein as surfactant by mass ratio, under stirring condition, slowly be added dropwise in the dispersant mixed aqueous solution C that newly makes, the volume ratio of solution C and dispersant kerosene 1: 10, be warming up to 70 ℃ after being added dropwise to complete, be incubated and stop heating after 10 minutes and stir gel precipitation is come out.Centrifugation obtains spherical xerogel presoma.The xerogel presoma is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains mixing the spherical LiFePO 4 product of niobium.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.95g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 160mAh/g.
Embodiment 4
With the 0.1875g ammonium niobium oxalate (titanium/lithium=0.01, mol ratio) among the 0.095g titanium tetrachloride replacement embodiment 3, other condition obtains doped titanium spherical LiFePO 4 product with embodiment 3.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.94g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 158mAh/g.
Embodiment 5
With the 0.1875g ammonium niobium oxalate (zirconium/lithium=0.01, mol ratio) among the 0.1521g seven water zirconium oxychlorides replacement embodiment 3, other condition obtains mixing the spherical LiFePO 4 product of zirconium with embodiment 3.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.94g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 158mAh/g.
Embodiment 6
With the 0.1875g ammonium niobium oxalate (magnesium/lithium=0.01, mol ratio) among the 0.074g magnesium nitrate replacement embodiment 3, other condition obtains mixing the spherical LiFePO 4 product of magnesium with embodiment 3.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.92g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 157mAh/g.
Embodiment 7
With the 0.1875g ammonium niobium oxalate (aluminium/lithium=0.01, mol ratio) among the 0.1065g aluminum nitrate replacement embodiment 3, other condition obtains mixing the spherical LiFePO 4 product of aluminium with embodiment 3.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.92g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 157mAh/g.
Embodiment 8
With the 0.1875g ammonium niobium oxalate (sucrose/LiFePO4=0.05, mass ratio) among the 0.395g sucrose replacement embodiment 3, other condition obtains the spherical LiFePO 4 product of carbon dope with embodiment 3.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.90g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 157mAh/g.
Embodiment 9
With the 0.1875g ammonium niobium oxalate (glucose/LiFePO4=0.05, mass ratio) among the 0.395g glucose replacement embodiment 3, other condition obtains the spherical LiFePO 4 product of carbon dope with embodiment 3.Recording this product average grain diameter is 6-7 μ m, and tap density is 1.90g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 157mAh/g.
Embodiment 10
Heat treatment temperature is 900 ℃, constant temperature 48 hours, and other condition obtains mixing the spherical LiFePO 4 product of niobium with embodiment 3.Recording this product average grain diameter is 5-6 μ m, and tap density is 2.0g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 150mAh/g.
Embodiment 11
Heat treatment temperature is 600 ℃, constant temperature 8 hours, and other condition obtains mixing the spherical LiFePO 4 product of niobium with embodiment 3.Recording this product average grain diameter is 7-8 μ m, and tap density is 1.8g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 145mAh/g.
Comparing embodiment 1
Adopt traditional mechanical mixture-high-temperature solid phase reaction method to prepare the non-ball shape ferric phosphate lithium.Take by weighing 18.5 gram lithium carbonate (Li
2CO
3), 90 gram ferrous oxalate (FeC
2O
42H
2O), 59.5 gram ammonium dihydrogen phosphate (NH
4H
2PO
4), place the ball mill ball milling to stop after 24 hours.Mixed material is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains non-ball shape ferric phosphate lithium product.Recording this product average grain diameter is 5-7 μ m, and tap density is 1.08g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 110mAh/g.
Comparing embodiment 2
Adopt traditional mechanical mixture-high-temperature solid phase reaction method preparation to mix the non-ball shape ferric phosphate lithium of niobium.Take by weighing 18.5 gram lithium carbonate (Li
2CO
3), 90 gram ferrous oxalate (FeC
2O
42H
2O), 59.5 gram ammonium dihydrogen phosphate (NH
4H
2PO
4), 1.875 the gram ammonium niobium oxalates (niobium/lithium=0.01, mol ratio), place the ball mill ball milling to stop after 24 hours.Mixed material is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains mixing the non-ball shape ferric phosphate lithium product of niobium.Recording this product average grain diameter is 5-7 μ m, and tap density is 1.10g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 119mAh/g.
Comparing embodiment 3
Adopt traditional mechanical mixture-high-temperature solid phase reaction method to prepare the non-ball shape ferric phosphate lithium of carbon dope.Take by weighing 18.5 gram lithium carbonate (Li
2CO
3), 90 gram ferrous oxalate (FeC
2O
42H
2O), 59.5 gram ammonium dihydrogen phosphate (NH
4H
2PO
4), 3.95 the gram sucrose (sucrose/LiFePO4=0.05, mass ratio), place the ball mill ball milling to stop after 24 hours.Mixed material is put into alumina crucible, speed by 200 ℃/hour in tube furnace is warming up to 800 ℃, constant temperature 16 hours, stop heating, in stove, naturally cool to room temperature, continue to feed the mist of 90% nitrogen+10% hydrogen in this process in the tube furnace, gas flow is 1 liter/minute, obtains the non-ball shape ferric phosphate lithium product of carbon dope.Recording this product average grain diameter is 5-7 μ m, and tap density is 0.98g/cm
3With the lithium sheet is negative pole, and recording this LiFePO4 first discharge specific capacity at room temperature is 118mAh/g.
Claims (3)
1. the preparation method of a high-density spherical ferric lithium phosphate, it is characterized in that: the technology of described preparation spherical LiFePO 4 comprises following each step:
1) takes by weighing ferric nitrate, phosphoric acid, lithium acetate at 1: 1: 1 with mol ratio, be dissolved in deionized water, make the mixed aqueous solution A that three kinds of concentration of aqueous solution are ferric nitrate, phosphoric acid and the lithium acetate of 1～3mol/L;
2) be to take by weighing urea and hexamethylenetetramine at 1～5: 1 by mass ratio, add deionized water and make its dissolving that making concentration is the aqueous solution B of 200～400g/L;
3) in 5 ℃～10 ℃ temperature range and under the stirring condition, the B drips of solution is added in the A solution, make mixed aqueous solution C;
4) with kerosene be dispersant, in kerosene, add 0.1%～5% span80 as surfactant by mass ratio; With the 3rd) the mixed aqueous solution C that makes of step slowly is added dropwise in the dispersant volume ratio 1: 5～20 of solution C and dispersant kerosene under stirring condition; Be warming up to 70～80 ℃ after being added dropwise to complete, be incubated and stop heating after 10～20 minutes and stir, make mixed aqueous solution change colloidal sol into, and then change into gel precipitation and come out;
5) centrifugation of step 4) gained gel is obtained spherical xerogel presoma;
6) with the spherical xerogel presoma of step 5) gained be at flow 0.1～10 liter/minute 90% nitrogen+10% hydrogen mixed gas protected down, obtained spherical LiFePO 4 in 8～48 hours through 600～900 ℃ of high-temperature heat treatment.
2. high-density spherical doped metal ion method preparing phosphate iron lithium, it is characterized in that: just in the mixed aqueous solution A of claim 1 step 1) in molar ratio, the ratio of doping metals compound/lithium=0.5%～2% is mixed one or more the metallic compound in magnesium nitrate, aluminum nitrate, titanium tetrachloride, zirconium oxychloride or the ammonium niobium oxalate, and all the other steps are identical.
3. high-density spherical carbon dope method preparing phosphate iron lithium, it is characterized in that: just mix as the sucrose of carbon source or in the glucose one or more in the ratio of sucrose or glucose/LiFePO4=0.5wt%～15wt% in the mixed aqueous solution A of claim 1 step 1), all the other steps are identical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100001679A CN1299369C (en) | 2005-01-06 | 2005-01-06 | Method for preparing high-density spherical lithium iron phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100001679A CN1299369C (en) | 2005-01-06 | 2005-01-06 | Method for preparing high-density spherical lithium iron phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1632969A CN1632969A (en) | 2005-06-29 |
| CN1299369C true CN1299369C (en) | 2007-02-07 |
Family
ID=34852872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100001679A Expired - Fee Related CN1299369C (en) | 2005-01-06 | 2005-01-06 | Method for preparing high-density spherical lithium iron phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1299369C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005565A (en) * | 2010-11-06 | 2011-04-06 | 合肥国轩高科动力能源有限公司 | Method for preparing carbon-coated lithium iron phosphate nanoparticles |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389515C (en) * | 2005-11-04 | 2008-05-21 | 南开大学 | Ferrolithium phosphate and its compound metal phosphide electrode material and producing method thereof |
| CN100448772C (en) * | 2006-08-11 | 2009-01-07 | 广州市鹏辉电池有限公司 | High density ultrafine composite ferric lithium phosphate anode material and preparation method |
| CN101162776B (en) * | 2007-10-26 | 2010-06-02 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same |
| CN100595949C (en) * | 2008-02-26 | 2010-03-24 | 郑州瑞普生物工程有限公司 | Method for making positive material positive ferric phosphate of lithium battery |
| JP5376894B2 (en) | 2008-10-20 | 2013-12-25 | 古河電池株式会社 | Multi-component phosphoric acid lithium compound particles having an olivine structure, a method for producing the same, and a lithium secondary battery using the same as a positive electrode material |
| CN101941685B (en) * | 2009-07-09 | 2012-05-30 | 河南新飞科隆电源有限公司 | Preparation of spherical lithium iron phosphate material and lithium ion battery using spherical lithium iron phosphate material |
| CN101794879B (en) * | 2010-03-04 | 2012-07-25 | 上海电力学院 | Preparation method of iron phosphate lithium of lithium ion battery positive-electrode materials |
| CN101927991B (en) * | 2010-08-26 | 2012-06-06 | 中国科学院青岛生物能源与过程研究所 | Spherical phosphate compound |
| CN102683642A (en) * | 2011-03-15 | 2012-09-19 | 倍特利能源科技股份有限公司 | Synthesis method for preparing lithium ion battery composite cathode material with olivine lattice defect structure by using rheological phase method |
| CN102208686B (en) * | 2011-05-17 | 2013-09-18 | 江苏赛尔电池有限公司 | Power battery using double-network nano lithium iron phosphate as anode |
| CN102956884B (en) * | 2012-11-29 | 2015-04-15 | 四川大学 | Lithium-rich manganese-based material and preparation method thereof |
| CN103400985A (en) * | 2013-08-08 | 2013-11-20 | 武汉盛锂新能源科技有限公司 | Preparation method of nanowire lithium iron phosphate by microwave soft template method |
| CN113003556A (en) * | 2021-01-26 | 2021-06-22 | 万向一二三股份公司 | Preparation method of high-compaction lithium iron phosphate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041335A (en) * | 1988-09-22 | 1990-04-18 | 中国建筑材料科学研究院高技术陶瓷研究所 | Micro-emulsion method for preparing zirconium oxide powder |
| CN1103849A (en) * | 1993-12-15 | 1995-06-21 | 中国科学院化工冶金研究所 | Method for prepn. of ball shaped hydroxy-apatite with homogeneous precipitation |
| US5910382A (en) * | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
| EP1261050A1 (en) * | 2001-05-23 | 2002-11-27 | n.v. Umicore s.a. | Lithium transition-metal phosphate powder for rechargeable batteries |
| CN1410349A (en) * | 2002-11-28 | 2003-04-16 | 清华大学 | Preparation method of multicrystal LiFePO4 powder having olivine structure |
| CN1431147A (en) * | 2003-02-17 | 2003-07-23 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
-
2005
- 2005-01-06 CN CNB2005100001679A patent/CN1299369C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041335A (en) * | 1988-09-22 | 1990-04-18 | 中国建筑材料科学研究院高技术陶瓷研究所 | Micro-emulsion method for preparing zirconium oxide powder |
| CN1103849A (en) * | 1993-12-15 | 1995-06-21 | 中国科学院化工冶金研究所 | Method for prepn. of ball shaped hydroxy-apatite with homogeneous precipitation |
| US5910382A (en) * | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
| EP1261050A1 (en) * | 2001-05-23 | 2002-11-27 | n.v. Umicore s.a. | Lithium transition-metal phosphate powder for rechargeable batteries |
| CN1410349A (en) * | 2002-11-28 | 2003-04-16 | 清华大学 | Preparation method of multicrystal LiFePO4 powder having olivine structure |
| CN1431147A (en) * | 2003-02-17 | 2003-07-23 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005565A (en) * | 2010-11-06 | 2011-04-06 | 合肥国轩高科动力能源有限公司 | Method for preparing carbon-coated lithium iron phosphate nanoparticles |
| CN102005565B (en) * | 2010-11-06 | 2015-05-13 | 合肥国轩高科动力能源股份公司 | Method for preparing carbon-coated lithium iron phosphate nanoparticles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1632969A (en) | 2005-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1299369C (en) | Method for preparing high-density spherical lithium iron phosphate | |
| CN1305148C (en) | Method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate | |
| CN1305147C (en) | Method for preparing high-density spherical ferric lithium phosphate as anode material of lithium-ion battery | |
| CN109192953B (en) | High-rate spherical lithium iron phosphate carbon composite cathode material and preparation method thereof | |
| CN105470474B (en) | A kind of composite negative pole material of high-capacity lithium ion cell and preparation method thereof | |
| CN100502103C (en) | Core-shell type nano-scale carbon-covered iron lithium phosphate compound anode material and method for preparing the same | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN1280185C (en) | Preparation process of lithium ferrous phosphate for positive pole of lithium ion cell | |
| CN102024947B (en) | LiFePO4/Li-Al-O composite positive electrode material and preparation method thereof | |
| CN101081696A (en) | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof | |
| CN101237043A (en) | Method for making ferrous lithium phosphate/carbon compound material of high active disorderly ferric phosphate | |
| CN1907844A (en) | High density ultrafine composite ferric lithium phosphate anode material and preparation method | |
| CN102633300A (en) | Carbon-coated lithium titanate cathode material as well as preparation method and applications thereof | |
| CN111342023B (en) | Positive electrode material and preparation method and application thereof | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN103545508B (en) | A kind of lithium iron borate anode material of lithium ion battery and its preparation method | |
| CN1821065A (en) | Process for preparing high density spherical lithium ferric phosphate | |
| CN111777065A (en) | Graphite modified material for lithium ion battery and preparation method thereof | |
| CN110085854B (en) | Lithium vanadium phosphate cathode material and preparation method thereof | |
| CN1821064A (en) | Method for preparing high density lithium ferric phosphate by microwave heating | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application | |
| CN100483809C (en) | Method for producing ultra-fine LiFePO4/C of lithium ion battery anode material | |
| CN113690420A (en) | Nitrogen-sulfur doped silicon-carbon composite material and preparation method and application thereof | |
| CN109980221A (en) | A kind of anode material for high-voltage lithium ion and its preparation method and application | |
| CN101593832A (en) | The process for preparing sol-gel of lithium ferrous phosphate as anode material of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070207 Termination date: 20190106 |