CN102205955A - Preparation method for battery anode material LiMPO4 - Google Patents
Preparation method for battery anode material LiMPO4 Download PDFInfo
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- CN102205955A CN102205955A CN 201110073404 CN201110073404A CN102205955A CN 102205955 A CN102205955 A CN 102205955A CN 201110073404 CN201110073404 CN 201110073404 CN 201110073404 A CN201110073404 A CN 201110073404A CN 102205955 A CN102205955 A CN 102205955A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910001305 LiMPO4 Inorganic materials 0.000 title abstract 7
- 239000010405 anode material Substances 0.000 title abstract 2
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000009388 chemical precipitation Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 29
- 229910013275 LiMPO Inorganic materials 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 150000003016 phosphoric acids Chemical class 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001311 chemical methods and process Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- IEMMJPTUSSWOND-UHFFFAOYSA-N lithium;nitrate;trihydrate Chemical compound [Li+].O.O.O.[O-][N+]([O-])=O IEMMJPTUSSWOND-UHFFFAOYSA-N 0.000 claims description 2
- NKEPWRHODHQIRS-UHFFFAOYSA-N lithium;sulfuric acid;hydrate Chemical compound [Li].O.OS(O)(=O)=O NKEPWRHODHQIRS-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 12
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910015818 MPO4 Inorganic materials 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000010450 olivine Substances 0.000 abstract 1
- 229910052609 olivine Inorganic materials 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 10
- -1 LiMnPO 4 Chemical class 0.000 description 6
- 229910010710 LiFePO Inorganic materials 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910013086 LiNiPO Inorganic materials 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910011841 LiFe0.1Mn0.9PO4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for a battery anode material LiMPO4. The method comprises the following steps of: preparing phosphate MPO4 by a chemical precipitation method; embedding lithium ions into crystals of the prepared phosphate MPO4 by a chemical method to form lithium-containing phosphate LiMPO4; and calcining the prepared lithium-containing phosphate LiMPO4 under the protection of inert gas at the temperature of lower than 600 DEG C, and converting the calcined lithium-containing phosphate LiMPO4 into olivine type lithium-containing phosphate LiMPO4 with a good crystal structure. By the preparation method, a process is simple, raw materials are readily available and cost is low; and the obtained LiMPO4 is nanoparticles with uniform particle sizes, has higher multiplying power performance and can improve the power performance of batteries and improve the energy density of the batteries when used for ion batteries.
Description
Technical field
The present invention relates to a kind of cell positive material LiMPO
4The preparation method, belong to electrochemical field.
Background technology
In recent years, oil price is progressively soaring to be increased the weight of day by day with urban atmospheric pollution, brought heavy pressure for people's production, life, traditional fuel-engined vehicle mode of transportation is subjected to increasing people and queries, development becomes people's common recognition to the low and eco-friendly new traffic tool of the dependency of traditional fossil energy.Therefore, countries in the world have all given great support to the development of electromobile, and have formulated corresponding evolutionary operation(EVOP), and expectation is alleviated more and more serious energy dilemma and air environmental pollution problem with this.At present, large-scale lithium ion battery is considered to the automobile power cell of potentialization.Domestic and international many automobile production producer is getting down to the research of automobile-used lithium ion battery, and has realized the part commercialization.LiFePO 4 material because have that security is good, cycle performance is excellent, characteristics such as environmental friendliness, raw material resources are abundant, be acknowledged as the first-selected positive electrode material of automobile-used lithium-ion-power cell of new generation, become each national research emphasis and developing direction in the world today.Except iron lithium phosphate, other li-contained phosphates such as LiMnPO
4, LiCoPO
4, LiNiPO
4, LiFe
xMn
1-xPO
4Also can be used as next large-scale lithium ion battery.
But except above advantage, the li-contained phosphate positive electrode material also has inborn shortcoming.Li-contained phosphate often has poor ionic conductance and electronic conductance, and this makes that the high rate performance of this class material is not good.In the past few years, suitable solution is all being sought by each big manufacturer.Theoretically, the nanometer of material granule is the effective solution of this shortcoming.Nanoscale can reduce lithium ion and the evolving path of electronics in charge and discharge process effectively, thereby promotes the multiplying power property of material.Yet, the synthetic particle scale nanometer that is difficult to realize li-contained phosphate of sending out of traditional high temperature solid-state.High temperature solid-state method synthesis technique is simple, after only needing lithium source and metal ion source M (M is one or more among Fe, Co, Mn, the Ni) and source of phosphoric acid material thorough mixing with the chemical formula proportioning, in 700 ℃～800 ℃ scopes, calcine got final product in 12～48 hours product.But the material of this method preparation, generally at tens microns, its multiplying power property can not satisfy high power lithium ion cell to particle size, the especially requirement of power cell.Nearly 2 years, synthetic being widely studied of carbon containing li-contained phosphate positive electrode material.The preparation of this class carbon containing li-contained phosphate is similar with traditional high temperature solid-state synthetic method.Difference is to add an amount of organism in the precursor of preparation li-contained phosphate, as sucrose, glucose etc.Then, under the protection of rare gas element, carry out high-temperature calcination.In the process of pyroprocessing, organic carbide can stop the li-contained phosphate particle to be grown up.In addition, the organic char-forming material surface electronic electricity that can improve li-contained phosphate is led.Therefore, contain carbon content lithium phosphoric acid salt and have multiplying power property preferably, and adopted by a plurality of manufacturer.But the carbon material in the carbon containing li-contained phosphate will reduce the density of electrode materials greatly.This be because the density of carbon material much smaller than the density of li-contained phosphate self.When this type of carbonaceous material is used to lithium ion battery, will reduces electrode density greatly, thereby reduce cell integrated energy density.
Summary of the invention
In view of the defective that above-mentioned prior art exists, it is simple to the objective of the invention is to propose a kind of technology, can access good rate capability and be the LiMPO of nano-scale particle
4Cell positive material LiMPO
4The preparation method.
Purpose of the present invention will be achieved by the following technical programs:
A kind of cell positive material LiMPO
4The preparation method, described M is selected from one or several among Fe, Mn, Co and the Ni, comprises the steps:
(a) method by chemical precipitation prepares phosphoric acid salt MPO
4
(b) lithium ion is embedded into the phosphoric acid salt MPO of above-mentioned preparation by chemical process
4Crystal in, form li-contained phosphate LiMPO
4
(c) with the li-contained phosphate MPO of above-mentioned preparation
4Under protection of inert gas and be lower than under 600 ℃ the condition and carry out calcination processing, be converted into olivine-type li-contained phosphate LiMPO with good crystalline structure
4, resulting LiMPO
4Be the nano-scale particle of yardstick homogeneous, its particle diameter is all less than 500nm.
Further, step (a) comprises following process: will contain M
3+The aqueous solution be added drop-wise to and contain PO
4 3-The aqueous solution in, form MPO
4Precipitation is with described MPO
4Precipitation after filtration, obtain MPO after washing and the drying treatment
4Pressed powder.
Further, step (b) comprises following process: with described MPO
4Pressed powder is distributed in the aqueous solution that contains lithium ion, and under powerful condition of stirring, the aqueous solution that will contain hydroborates is added drop-wise to the above-mentioned pressed powder MPO that disperseed lentamente then
4, and contain in the aqueous solution of lithium ion, chemical reaction: 4Li takes place
++ 4MPO
4+ BH
4 -+ 4H
2O → 4LiMPO
4+ BO
2 -+ H
2+ 4H
+, after reaction finishes, with reaction solution after filtration, obtain the phosphoric acid salt LiMPO of embedding lithium after washing and the vacuum drying treatment
4
Further, the described aqueous solution that contains lithium ion is the aqueous solution that is selected from one or more compounds in lithium hydroxide, lithium chloride, Lithium Acetate, Quilonum Retard, lithium nitrate, nitrate trihydrate lithium, Lithium Sulphate and the sulfuric acid monohydrate lithium.
Further, described hydroborates is selected from NaBH
4, KBH
4, LiBH
4In one or more.
Further, rare gas element is nitrogen and/or argon gas described in the step (c).
Compared with prior art, beneficial effect of the present invention is: (1) technology is simple, starting material are easily obtained, and cost is lower; (2) resulting LiMPO
4Be the nano-scale particle of yardstick homogeneous, have high rate performance preferably; (3) resulting LiMPO
4Be used for the power-performance that ionization cell can improve battery, improve the energy density of battery.
Embodiment
Below in conjunction with embodiment technical solution of the present invention is elaborated.
Embodiment 1
With FeCl
3The aqueous solution under stirring condition, be added drop-wise to NH lentamente
4H
2PO
4The aqueous solution in, reaction obtains FePO
4Precipitation is with resulting FePO
4Precipitation after filtration, obtain FePO after washing and the drying treatment
4Pressed powder; With the above-mentioned FePO that obtains
4Pressed powder is distributed to and contains LiNO
3The aqueous solution in, in this solution, progressively dripping NaBH under the powerful condition of stirring
4The aqueous solution, following chemical reaction: 4Li takes place in this course
++ 4FePO
4+ BH
4 -+ 4H
2O → 4LiFePO
4+ BO
2 -+ 2H
2+ 4H
+After reaction finishes, reaction solution is obtained the phosphoric acid salt LiFePO of embedding lithium through filtration, washing and vacuum drying treatment
4The phosphoric acid salt LiFePO of the embedding lithium of above-mentioned preparation
4Be direct synthetic in the aqueous solution at room temperature, do not have good crystalline structure, under argon shield, under 600 ℃ of conditions, calcine the nanometer li-contained phosphate LiFePO that just can obtain having the well-defined crystal structure in 5～24 hours
4
The nano level LiFePO that obtains by method for preparing
4Particle, its granular size is between 100nm～200nm.With the LiFePO for preparing
4Nano particle, conductive agent and binding agent are mixed into slurry according to 85: 5: 10 mass ratio, and the slurry that mixes is coated on the aluminum foil current collector with certain thickness.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio is 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 162mAh/g; When 1C charged and discharged, its capacity was 145mAh/g; When 20C charged and discharged, the capacity of this material was 115mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 97%.
Embodiment 2
Prepare nanometer LiMnPO according to the method among the embodiment 1
4Particle (not repeating them here), resulting LiMnPO
4Granular size is between 100nm～300nm.With the LiMnPO that makes
4Nano particle, conductive agent and binding agent are mixed into slurry according to 85: 5: 10 mass ratio, and the slurry that mixes is coated on the aluminum foil current collector with certain thickness.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 143mAh/g; When 1C charged and discharged, its capacity was 123mAh/g; When 20C charged and discharged, the capacity of this material was 75mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 82%.
Embodiment 3
Prepare nanometer LiCoPO according to the method among the embodiment 1
4Particle (not repeating them here), resulting LiCoPO
4Granular size is between 100nm～200nm.With the LiCoPO that makes
4Particle, conductive agent and binding agent are mixed into slurry according to 85: 5: 10 mass ratio, and the slurry that mixes is coated on the aluminum foil current collector with certain thickness.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 120mAh/g; When 1C charged and discharged, its capacity was 106mAh/g; When 20C charged and discharged, the capacity of this material was 68mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 70%.
Embodiment 4
Prepare nanometer LiNiPO according to the method among the embodiment 1
4Particle (not repeating them here), resulting LiNiPO
4Granular size is between 200nm～400nm.With the LiNiPO that makes
4Nano particle, conductive agent and binding agent are coated the slurry that mixes on the aluminum foil current collector with certain thickness according to 85: 5: 10 mixed form slurry.With 1.0mol/L LiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 68mAh/g; When 1C charged and discharged, its capacity was 50mAh/g; When 20C charged and discharged, the capacity of this material was 25mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 50%.
Embodiment 5
Prepare nanometer LiFe according to the method among the embodiment 1
0.1Mn
0.9PO
4Particle (not repeating them here), resulting LiFe
0.1Mn
0.9PO
4Granular size is between 100nm～300nm.With the LiFe that makes
0.1Mn
0.9PO
4Particle, conductive agent and binding agent are coated the slurry that mixes on the aluminum foil current collector with certain thickness according to 85: 5: 10 mixed form slurry.With 1.0mol/LLiPF
6/ EC+DEC+DMC (volume ratio 1: 1: 1) is an ionogen, and the Li sheet is a negative pole, and it is barrier film that the U.S. produces Cellgard-2400 type polypropylene screen, is assembled into button cell in being full of the glove box of argon gas.On the LandCT2001A type battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, synthetic materials is carried out multiplying power test and cycle life test then.When 1/3C charged and discharged, the capacity of this material was 152mAh/g; When 1C charged and discharged, its capacity was 135mAh/g; When 20C charged and discharged, the capacity of this material was 105mAh/g.Under the 1C condition, charge and discharge 100 weeks of circulation, the capacity sustainment rate is 90%.
Sum up the performance number of the various materials that make among the embodiment 1～5 below with the form of form.
The performance perameter of the various materials that make among table 1 embodiment 1～5
Compared with prior art, beneficial effect of the present invention is: (1) technology is simple, starting material are easily obtained, and cost is lower; (2) resulting LiMPO
4Be the nano-scale particle of yardstick homogeneous, have high rate performance preferably; (3) resulting LiMPO
4Be used for the power-performance that ionization cell can improve battery, improve the energy density of battery.
The present invention still has multiple concrete embodiment, and all employings are equal to replacement or equivalent transformation and all technical schemes of forming, all drop within the scope of protection of present invention.
Claims (6)
1. cell positive material LiMPO
4The preparation method, described M is selected from one or several among Fe, Mn, Co and the Ni, it is characterized in that: comprise the steps:
(a) method by chemical precipitation prepares phosphoric acid salt MPO
4
(b) lithium ion is embedded into the phosphoric acid salt MPO of above-mentioned preparation by chemical process
4Crystal in, form li-contained phosphate LiMPO
4
(c) with the li-contained phosphate MPO of above-mentioned preparation
4Under protection of inert gas and be lower than under 600 ℃ the condition and carry out calcination processing, be converted into olivine-type li-contained phosphate LiMPO with good crystalline structure
4
2. cell positive material LiMPO according to claim 1
4The preparation method, it is characterized in that: step (a) comprises following process: will contain M
3+The aqueous solution be added drop-wise to and contain PO
4 3-The aqueous solution in, form MPO
4Precipitation is with described MPO
4Precipitation after filtration, obtain MPO after washing and the drying treatment
4Pressed powder.
3. cell positive material LiMPO according to claim 2
4The preparation method, it is characterized in that: step (b) comprises following process: with described MPO
4Pressed powder is distributed in the aqueous solution that contains lithium ion, and under powerful condition of stirring, the aqueous solution that will contain hydroborates is added drop-wise to the above-mentioned pressed powder MPO that disperseed lentamente then
4, and contain in the aqueous solution of lithium ion, chemical reaction: 4Li takes place
++ 4MPO
4+ BH
4 -+ 4H
2O → 4LiMPO
4+ BO
2 -+ H
2+ 4H
+, after reaction finishes, with reaction solution after filtration, obtain the phosphoric acid salt LiMPO of embedding lithium after washing and the vacuum drying treatment
4
4. cell positive material LiMPO according to claim 3
4The preparation method, it is characterized in that: the described aqueous solution that contains lithium ion is the aqueous solution that is selected from one or more compounds in lithium hydroxide, lithium chloride, Lithium Acetate, Quilonum Retard, lithium nitrate, nitrate trihydrate lithium, Lithium Sulphate and the sulfuric acid monohydrate lithium.
5. cell positive material LiMPO according to claim 4
4The preparation method, it is characterized in that: described hydroborates is selected from NaBH
4, KBH
4, LiBH
4In one or more.
6. cell positive material LiMPO according to claim 5
4The preparation method, it is characterized in that: rare gas element is nitrogen and/or argon gas described in the step (c).
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|---|---|---|---|
| CN 201110073404 CN102205955A (en) | 2011-03-25 | 2011-03-25 | Preparation method for battery anode material LiMPO4 |
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|---|---|---|---|
| CN 201110073404 CN102205955A (en) | 2011-03-25 | 2011-03-25 | Preparation method for battery anode material LiMPO4 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039693A (en) * | 2011-12-21 | 2014-09-10 | 化学制造布敦海姆两合公司 | Metal phosphate containing manganese and method for its production |
| CN104779390A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院宁波材料技术与工程研究所 | Spheroidic nanometer manganous-lithium phosphate and its preparation method and use |
| CN105932324A (en) * | 2016-06-24 | 2016-09-07 | 双登集团股份有限公司 | Cobalt lithium phosphate positive electrode material and preparation method therefor |
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| CN104039693A (en) * | 2011-12-21 | 2014-09-10 | 化学制造布敦海姆两合公司 | Metal phosphate containing manganese and method for its production |
| US9350020B2 (en) | 2011-12-21 | 2016-05-24 | Chemische Fabrik Budenheim Kg | Metal phosphate containing manganese and method for its production |
| CN104039693B (en) * | 2011-12-21 | 2017-03-01 | 化学制造布敦海姆两合公司 | Phosphate containing manganese Metal and preparation method thereof |
| CN104779390A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院宁波材料技术与工程研究所 | Spheroidic nanometer manganous-lithium phosphate and its preparation method and use |
| CN104779390B (en) * | 2014-01-15 | 2017-11-14 | 中国科学院宁波材料技术与工程研究所 | Spherical nano lithium manganese phosphate of lithium and its preparation method and application |
| CN105932324A (en) * | 2016-06-24 | 2016-09-07 | 双登集团股份有限公司 | Cobalt lithium phosphate positive electrode material and preparation method therefor |
| CN116265386A (en) * | 2021-12-16 | 2023-06-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of phosphate cathode material |
| CN114715872A (en) * | 2022-04-29 | 2022-07-08 | 邱双 | Preparation of LiMPO4Method for producing powder material |
| CN114715872B (en) * | 2022-04-29 | 2024-05-28 | 邱双 | Preparation of LiMPO4Method for preparing powder material |
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