CN100595949C - Method for making positive material positive ferric phosphate of lithium battery - Google Patents
Method for making positive material positive ferric phosphate of lithium battery Download PDFInfo
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- CN100595949C CN100595949C CN200810049265A CN200810049265A CN100595949C CN 100595949 C CN100595949 C CN 100595949C CN 200810049265 A CN200810049265 A CN 200810049265A CN 200810049265 A CN200810049265 A CN 200810049265A CN 100595949 C CN100595949 C CN 100595949C
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- ferric
- portions
- lithium battery
- hydrogen peroxide
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims description 32
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims description 32
- 239000000463 material Substances 0.000 title claims description 20
- 239000005955 Ferric phosphate Substances 0.000 title claims description 11
- 229940032958 ferric phosphate Drugs 0.000 title claims description 11
- 238000000034 method Methods 0.000 title abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 2
- 235000011007 phosphoric acid Nutrition 0.000 abstract 6
- 239000000243 solution Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
Classifications
-
- 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
Abstract
The present invention discloses a preparation method for ferric orthophosphoric acid which is lithium battery anode material, using 100 portions of ferrous sulfate heptahydrate, 41.8-48.8 portions ofphosphoric acid, 21.8-38.5 portions of hydrogen peroxide or 6.36-10.0 portions of sodium chlorate, 12.0-12.5 portions of sodium hydroxide or 15.0-18.0 portions of sodium carbonate and 500-1000 portions of water for preparation. The ferrous sulfate heptahydrate, the phosphoric acid and the water are compounded into solution in a reaction vessel; the hydrogen peroxide or the sodium chlorate is addedinto the solution; the temperature of the solution is 50-55 DEG C, and the sodium hydroxide or the sodium carbonate is added into the solution under the condition of stirring; then the solution temperature is increased to be between 85 DEG C and 95 DEG C; the temperature is kept for 5-15 hours, and in the meantime, the solution is led into a swirler to be separated till the sulfate radical content in products is less than 0.2 percent; the solution is cooled to be at 50 DEG C for carrying out the solid-liquid separation of the products and liquid; the particle diameter of obtained ferric orthophosphoric acid is 1-2 mu m; the specific surface area of the ferric orthophosphoric acid is 48-55.5m2/g; the tap density of the ferric orthophosphoric acid is greater than 1.6g/cm3. When the ferric orthophosphoric acid prepared with the method is used as raw material for preparing lithium iron phosphate via solid phase synthesis, the lithium battery anode material with excellent performance can be obtained.
Description
Technical field
The present invention relates to lithium battery material, especially relate to the preparation method of positive material positive ferric phosphate of lithium battery.
Background technology
The exploitation of clean energy resource is one of key areas of the primary development in the whole world with building, and battery is the important media of these new forms of energy of rational and efficient use.Lithium ion battery has obtained swift and violent development in the light current industry, and the research and development of dynamic lithium battery reaches its maturity, and the development of electric automobile (EV) will bring revolutionary variation to the improvement of people's environment.The key technology of electric automobile manufacturing is a battery problems, studies show that lithium battery is the first-selected battery of electric powered motor, and the key technology of preparation dynamic lithium battery then is battery material, especially LiFePO 4 of anode material.
The preparation of LiFePO4 is at present adopted with the ferric orthophosphate more and is carried out solid phase synthesis for the predecessor raw material.Because in the high-temperature reaction process of preparation LiFePO4, the diffusion of ion is a slow process, so the activity of ferric orthophosphate has material impact to reaction, particularly prepared in batches.The ferric orthophosphate distribution of particles of using existing production method to produce is wide, agglomeration is more serious between particle, cause surface activity lower, be used to prepare lithium cell anode material of lithium iron phosphate, the secondary cell specific capacity that makes is less, and unstable product quality has directly limited the scope of application of lithium battery.
Summary of the invention
The object of the invention is to provide a kind of distribution of particles narrow, and particle diameter is little, is uniformly dispersed, the preparation method who is used for positive material positive ferric phosphate of lithium battery that reactivity is high.
For achieving the above object, the present invention can take following technical proposals:
The preparation method who is used for positive material positive ferric phosphate of lithium battery of the present invention is prepared from by major ingredient ferrous sulfate heptahydrate, phosphoric acid, hydrogen peroxide or sodium chlorate, NaOH or sodium carbonate and auxiliary material water:
The weight portion proportioning of a, reactant is:
Ferrous sulfate heptahydrate: 100;
Phosphoric acid: 41.8-48.8;
Hydrogen peroxide: 21.8-38.5 or sodium chlorate: 6.36-10.0;
NaOH: 12.0-12.5 or sodium carbonate: 15.0-18.0;
Water: 500-1000;
B, step:
The first step, in reactor, ferrous sulfate heptahydrate, phosphoric acid, water are mixed with solution; Add hydrogen peroxide or sodium chlorate then in described solution, control solution temperature simultaneously between 50 ℃-55 ℃, stirring condition adds NaOH or sodium carbonate down, and reaction solution is highly acid;
Second goes on foot, first step gained solution is warmed up between 85 ℃-95 ℃, be incubated 5-15 hour, in insulation time, introduces solution and is separated in the product sulfate radical content in the swirler less than 0.2%, be cooled to 50 ℃ of Separation of Solid and Liquid of carrying out product and liquid then, separated products is drying to obtain ferric orthophosphate; The particle diameter of gained ferric orthophosphate is 1-2 μ m, and specific area is 48-55.5m
2/ g; Tap density is greater than 1.6g/cm
3
Described phosphoric acid concentration is 85%; Described hydrogen peroxide concentration is 28%.
The ferric orthophosphate average grain diameter that the invention has the advantages that preparation is 1-2 μ m, and specific area is 48-55.5m/g.Observe under the high power electron microscope, product is the sphere of rough surface, gauffer, has improved the activity of ferric orthophosphate greatly.Ferric orthophosphate with this method preparation is that raw material prepares LiFePO4 through solid phase synthesis, the anode material for lithium-ion batteries that available can be good, and the secondary cell specific capacity that makes with this positive electrode is greater than 130mAh/g, and tap density is greater than 1.6g/cm
3, improved the performance of lithium battery greatly, expanded the scope of application of ferric orthophosphate.
Embodiment
Embodiment 1:
The preparation method who is used for positive material positive ferric phosphate of lithium battery of the present invention, carry out according to following step:
At 1m
3Enamel reaction still in add 150kg water, 27.5kg ferrous sulfate heptahydrate, make the solid dissolving under stirring, add 12.5kg phosphoric acid, adding 9kg concentration is 28% hydrogen peroxide in when 1h, make the ferrous iron in the solution be converted into ferric iron fully, adjusting solution temperature is 55 ℃, adding concentration is 10% sodium carbonate liquor 47kg under stirring, flow velocity is 10L/h, be warming up to 95 ℃ of insulation 6h then, will separate soluble inorganic salt in 6 grades of swirlers of solution introducing in the time of insulation, product forms the particulate of spheroidal at swirler high speed eddy flow simultaneously; Be separated in the product sulfate radical content less than after 0.2%, be cooled to 50 ℃ product and liquid carried out the solid-liquid centrifugation, the separated products drying is handled and is promptly got ferric orthophosphate; Gained ferric orthophosphate product particle diameter is 1-2 μ m, and specific area is 55.5m
2/ g; Tap density is greater than 1.6g/cm
3
Embodiment 2:
The preparation method who is used for positive material positive ferric phosphate of lithium battery of the present invention, carry out according to following step:
At 10m
3Enamel reaction still in add 3000kg water, the 570kg ferrous sulfate heptahydrate, make the solid dissolving under stirring, add 250kg phosphoric acid then, adding 185kg concentration is 28% hydrogen peroxide in when 1h, make the ferrous iron in the solution be converted into ferric iron fully, adjusting solution temperature is 50 ℃, adding concentration is 10% sodium carbonate liquor 950kg under stirring, flow velocity is 200L/h, be warming up to 85 ℃ of insulation 15h, will separate soluble inorganic salt in 6 grades of swirlers of solution introducing in the time of insulation, product forms the particulate of spheroidal at swirler high speed eddy flow simultaneously; Be separated in the product sulfate radical content less than after 0.2%, be cooled to 50 ℃ product and liquid carried out the solid-liquid centrifugation, the separated products drying handle high activity material ferric orthophosphate; Gained ferric orthophosphate product particle diameter is 1-2 μ m, and specific area is 51.60m
2/ g; Tap density is greater than 1.6g/cm
3
Embodiment 3:
The preparation method who is used for positive material positive ferric phosphate of lithium battery of the present invention, carry out according to following step:
At 10m
3Enamel reaction still in add 3000kg water, the 570kg ferrous sulfate heptahydrate, make the solid dissolving under stirring, add 250kg phosphoric acid then, add the aqueous solution that contains 40kg sodium chlorate in when 1h, make the ferrous iron in the solution be converted into ferric iron fully, adjusting solution temperature is 50 ℃, adding concentration is 10% sodium carbonate liquor 950kg under stirring, flow velocity is 200L/h, be warming up to 90 ℃ of insulation 8h then, will separate soluble inorganic salt in 6 grades of swirlers of solution introducing in the time of insulation, product forms the particulate of spheroidal at swirler high speed eddy flow simultaneously; Be separated in the product sulfate radical content less than after 0.2%, be cooled to 50 ℃ product and liquid carried out the solid-liquid centrifugation, the separated products drying handle high activity material ferric orthophosphate; Gained ferric orthophosphate product particle diameter is 1-2 μ m, and specific area is 49.2m
2/ g; Tap density is greater than 1.6g/cm
3
Embodiment 4:
The preparation method who is used for positive material positive ferric phosphate of lithium battery of the present invention, carry out according to following step:
At 10m
3Enamel reaction still in add 3000kg water, the 570kg ferrous sulfate heptahydrate, make the solid dissolving under stirring, add 250kg phosphoric acid, add the 185kg hydrogen peroxide in when 1h, make the ferrous iron in the solution be converted into ferric iron fully, adjusting solution temperature is 52 ℃, adding concentration is 10% sodium hydroxide solution 704kg under stirring, flow velocity is 200L/h, be warming up to 93 ℃ of insulation 10h then, will separate soluble inorganic salt in 6 grades of swirlers of solution introducing in the time of insulation, product forms the particulate of spheroidal at swirler high speed eddy flow simultaneously; Be separated in the product sulfate radical content less than after 0.2%, be cooled to 50 ℃ product and liquid carried out the solid-liquid centrifugation, the separated products drying handle high activity material ferric orthophosphate; Gained ferric orthophosphate product particle diameter is 1-2 μ m, and specific area is 48.50m
2/ g; Tap density is greater than 1.6g/cm
3
Embodiment 5:
The preparation method who is used for positive material positive ferric phosphate of lithium battery of the present invention carries out according to following step: at 10m
3Enamel reaction still in add 3000kg water, the 570kg ferrous sulfate heptahydrate, make the solid dissolving under stirring, add 250kg phosphoric acid, add the aqueous solution that contains 40kg sodium chlorate in when 1h, make the ferrous iron in the solution be converted into ferric iron fully, adjusting solution temperature is 50 ℃, adding concentration is 10% sodium carbonate liquor 950kg under stirring, and flow velocity is 200L/h, and the pH value that makes solution is between 2-3; Be warming up to 90 ℃ of insulation 13h then, will separate soluble inorganic salt in 6 grades of swirlers of solution introducing in the time of insulation, product forms the particulate of spheroidal at swirler high speed eddy flow simultaneously; Be separated in the product sulfate radical content less than after 0.2%, be cooled to 50 ℃ product and liquid carried out the solid-liquid centrifugation, the separated products drying handle high activity material ferric orthophosphate; Gained ferric orthophosphate product particle diameter is 1-2 μ m, and specific area is 52.60m
2/ g; Tap density is greater than 1.6g/cm
3
Claims (1)
1, a kind of preparation method who is used for positive material positive ferric phosphate of lithium battery is characterized in that: it is prepared from by major ingredient ferrous sulfate heptahydrate, phosphoric acid, hydrogen peroxide or sodium chlorate, NaOH or sodium carbonate and auxiliary material water:
The weight portion proportioning of a, reactant is:
Ferrous sulfate heptahydrate: 100;
Phosphoric acid: 41.8-48.8;
Hydrogen peroxide: 21.8-38.5 or sodium chlorate: 6.36-10.0;
NaOH: 12.0-12.5 or sodium carbonate: 15.0-18.0;
Water: 500-1000;
B, step:
The first step, in reactor, ferrous sulfate heptahydrate, phosphoric acid, water are mixed with solution; Add hydrogen peroxide or sodium chlorate then in described solution, control solution temperature simultaneously between 50 ℃-55 ℃, stirring condition adds NaOH or sodium carbonate down, and reaction solution is highly acid;
Second goes on foot, first step gained solution is warmed up between 85 ℃-95 ℃, be incubated 5-15 hour, in insulation time, introduces solution and is separated in the product sulfate radical content in the swirler less than 0.2%, be cooled to 50 ℃ of Separation of Solid and Liquid of carrying out product and liquid then, separated products is drying to obtain ferric orthophosphate; The particle diameter of gained ferric orthophosphate is 1-2 μ m, and specific area is 48-55.5m
2/ g; Tap density is greater than 1.6g/cm
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810049265A CN100595949C (en) | 2008-02-26 | 2008-02-26 | Method for making positive material positive ferric phosphate of lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810049265A CN100595949C (en) | 2008-02-26 | 2008-02-26 | Method for making positive material positive ferric phosphate of lithium battery |
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| CN101237042A CN101237042A (en) | 2008-08-06 |
| CN100595949C true CN100595949C (en) | 2010-03-24 |
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| CN200810049265A Expired - Fee Related CN100595949C (en) | 2008-02-26 | 2008-02-26 | Method for making positive material positive ferric phosphate of lithium battery |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009001204A1 (en) * | 2009-02-26 | 2010-09-02 | Chemische Fabrik Budenheim Kg | Production of iron orthophosphate |
| KR101718918B1 (en) * | 2009-09-09 | 2017-03-22 | 도다 고교 가부시끼가이샤 | Ferric phosphate hydrate particle powder and process for production thereof, olivine-type lithium iron phosphate particle powder and process for production thereof, and non-aqueous electrolyte secondary battery |
| CN102030323B (en) * | 2010-11-30 | 2012-11-28 | 湖北兴发化工集团股份有限公司 | Preparation method of iron phosphate |
| CN102583293B (en) * | 2012-02-09 | 2014-01-01 | 昆明川金诺化工股份有限公司 | Preparation method of cell grade ferric orthophosphate |
| CN103208627B (en) * | 2013-02-22 | 2015-11-25 | 贵州安达科技能源股份有限公司 | A kind of ferric phosphate material and preparation method thereof |
| CN106517128A (en) * | 2016-11-08 | 2017-03-22 | 河南省净寰新能源科技有限公司 | Low-cost cell-grade ferric phosphate micro powder preparation method |
| CN107337189B (en) * | 2017-08-23 | 2019-09-20 | 江西艾德纳米科技有限公司 | The method of ferric phosphate continuous production system and continuous production ferric phosphate |
| CN107910547B (en) * | 2017-11-30 | 2020-09-22 | 深圳绿霆动力科技有限公司 | High-specific-capacity lithium ion battery positive electrode material and preparation method thereof |
| CN113247876A (en) * | 2021-04-30 | 2021-08-13 | 广东邦普循环科技有限公司 | Ferric phosphate precursor and preparation method and application thereof |
Citations (2)
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|---|---|---|---|---|
| CN1632969A (en) * | 2005-01-06 | 2005-06-29 | 清华大学 | Method for preparing high-density spherical lithium iron phosphate |
| CN1974411A (en) * | 2006-12-19 | 2007-06-06 | 中南大学 | Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production |
-
2008
- 2008-02-26 CN CN200810049265A patent/CN100595949C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632969A (en) * | 2005-01-06 | 2005-06-29 | 清华大学 | Method for preparing high-density spherical lithium iron phosphate |
| CN1974411A (en) * | 2006-12-19 | 2007-06-06 | 中南大学 | Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production |
Non-Patent Citations (2)
| Title |
|---|
| 正磷酸铁的合成及其性能的研究. 马广成等.《河北大学学报(自然科学版)》，第13卷第4期. 1993 |
| 正磷酸铁的合成及其性能的研究. 马广成等.《河北大学学报(自然科学版)》，第13卷第4期. 1993 * |
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