CN102437314A - Foam metal/lithium iron phosphate integral electrode with three-dimensional structure, preparation method thereof and lithium ion battery using integral electrode as positive pole piece - Google Patents
Foam metal/lithium iron phosphate integral electrode with three-dimensional structure, preparation method thereof and lithium ion battery using integral electrode as positive pole piece Download PDFInfo
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- CN102437314A CN102437314A CN2011104037247A CN201110403724A CN102437314A CN 102437314 A CN102437314 A CN 102437314A CN 2011104037247 A CN2011104037247 A CN 2011104037247A CN 201110403724 A CN201110403724 A CN 201110403724A CN 102437314 A CN102437314 A CN 102437314A
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- lifepo4
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- 239000006260 foam Substances 0.000 title claims abstract description 143
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 113
- 239000002184 metal Substances 0.000 title claims abstract description 113
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 83
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 150000002505 iron Chemical class 0.000 claims description 26
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- 230000004888 barrier function Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229930006000 Sucrose Natural products 0.000 claims description 12
- 239000005720 sucrose Substances 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 11
- 238000000518 rheometry Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 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 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 125000000185 sucrose group Chemical group 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 32
- 238000003487 electrochemical reaction Methods 0.000 abstract description 15
- 230000010287 polarization Effects 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 22
- 239000002994 raw material Substances 0.000 description 14
- 239000010439 graphite Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 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 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 239000012530 fluid Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
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- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a foam metal/lithium iron phosphate integral electrode with a three-dimensional structure, a preparation method thereof and a lithium ion battery using the integral electrode as a positive pole piece, relates to the foam metal/lithium iron phosphate integral electrode, the preparation method thereof and the lithium ion battery using the integral electrode as the positive pole piece, and solves the problem of high-rate poor charge-discharge performance, which still exists in a two-dimensional lithium iron phosphate electrode. The integral electrode is obtained by using foam metal as a support body and a current collector, generating nano lithium iron phosphate particles on the surface of the foam metal in situ and fixing the nano lithium iron phosphate particles on the surface of a foam metal framework. The invention provides the lithium ion battery using the integral electrode as the positive pole piece. By using the foam metal as the support body and the current collector, a three-dimensional stereo conductive network can be formed, so the electronic conductivity of materials and the superficial area of an electrochemical reaction are increased, the interface current density in the electrochemical reaction process is reduced, and electrochemical reaction polarization is decreased; and after the lithium ion battery is cycled for 40 times under a charge-discharge rate of 5C, the capacity retention ratio of the lithium ion battery is still above 90 percent.
Description
Technical field
The present invention relates to a kind of three-dimensional structure foam metal/LiFePO4 one electrode, its preparation method and be the lithium ion battery of anode pole piece with it.
Background technology
Lithium ion battery is the ideal source system that drives electric motor car and PHEV at present, and wherein, it is cheap that LiFePO4 has, Heat stability is good, and good cycle, advantages of environment protection is the optimal positive electrode of electrokinetic cell always.Yet still there is the problem of high rate charge-discharge poor-performing in present two-dimentional LiFePO4 electrode; Also difficult with satisfy the requirement of pure electric vehicle and plug-in hybrid electric vehicle to the battery fast charging and discharging, restricted its development aspect energy output and ev industry.
Summary of the invention
The objective of the invention is in order to solve the problem that still there is the high rate charge-discharge poor-performing in existing two-dimentional LiFePO4 electrode, the invention provides a kind of three-dimensional structure foam metal/LiFePO4 one electrode, its preparation method and be the lithium ion battery of anode pole piece with it.
Three-dimensional structure foam metal of the present invention/LiFePO4 one electrode is to be supporter and collector with the foam metal, and the nano-grade lithium iron phosphate particle generates and is fixed in that the skeleton surface of foam metal obtains at the foam metal surface in situ; Wherein, foam metal is that the thickness after roll extrusion is handled is the three-dimensional foam metal of 300 μ m～1000 μ m; Described nano-grade lithium iron phosphate particle generates and realize through following operation on the skeleton surface of being fixed in foam metal at the foam metal surface in situ: through trivalent iron salt, P source compound, Li source compound, organic molecule carbon source and deionized water are utilized rheology mutually the rheological body that obtains of method infiltrate to the space of foam metal and obtain three-dimensional precursor; Again with three-dimensional precursor sintering; Realize that the nano-grade lithium iron phosphate particle generates and be fixed in the skeleton surface of foam metal at the foam metal surface in situ; Wherein, Fe in the trivalent iron salt and the mol ratio of the P in the P source compound are 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1, and the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1.
The preparation method of three-dimensional structure foam metal of the present invention/LiFePO4 one electrode realizes through following steps: one, with foam metal carry out roll extrusion handle to thickness be 300 μ m～1000 μ m, ultrasonic cleaning in alcohol then, dry again; Two, the mol ratio by Fe in the trivalent iron salt and the P in the P source compound is 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing trivalent iron salt, Li source compound, P source compound and organic molecule carbon source; Then with the trivalent iron salt that takes by weighing, Li source compound, P source compound and organic molecule carbon source mix mixture; In mixture, add deionized water again, ultrasonic stirring obtained true solution in 2～4 hours, then true solution was placed to stir under 50～100 ℃ the temperature to form rheological body; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the foam metal after step 1 is handled is immersed in the rheological body that step 2 obtains, foam metal is taken out after being dried to constant weight then, three-dimensional precursor; Four, the three-dimensional precursor that step 3 is obtained places inert gas or reducibility gas special atmosphere oven; Predecomposition is 2～4 hours under 200 ℃～300 ℃ temperature; Be warming up to 550 ℃～650 ℃ then; Insulation calcining 5～12 hours is cooled to room temperature again, gets three-dimensional structure foam metal/LiFePO4 one electrode.
With three-dimensional structure foam metal of the present invention/LiFePO4 one electrode is the lithium ion battery of anode pole piece; Comprise positive plate, negative plate, barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in the periphery of positive plate, negative plate and barrier film, and wherein, positive plate is three-dimensional structure foam metal of the present invention/LiFePO4 one electrode.
Foam metal described in the present invention is nickel foam or foamed aluminium, and specific area is high, adopts the commercially available prod to get final product.
Trivalent iron salt described in the present invention is ferric nitrate and/or iron chloride; Said P source compound is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate; Said Li source compound is a kind of in lithium nitrate, lithium carbonate and the lithium hydroxide or several kinds of mixtures wherein, and said organic molecule carbon source is sucrose and/or glucose.
Adopt rheology phase method to be prepared into rheological body in the preparation method's of three-dimensional structure foam metal of the present invention/LiFePO4 one electrode the step 2; Rheology phase method is a kind of emerging existing method of synthesizing inorganic nonmetallic materials; This method is after solid reactant is mixed according to a certain percentage; Be dissolved in an amount of water or other solvents and form true solution, make liquid viscosity increase through heating or the mode that stirs then, form the rheological body that solids and liquid substance are evenly distributed.In rheological body, the surface energy of solia particle is utilized effectively, and solids contact with liquid substance closely, evenly, and heat exchange is good, is not easy to occur the local overheating phenomenon.Compare with high temperature solid-state synthetic method commonly used, this method has advantages such as synthesis temperature is low, and roasting time is short, and the gained material granule is little and be evenly distributed.Wherein, said rheological body is meant under the effect of stress, produces the object that flows with distortion.
Foam metal has good conductivity, and specific area is big, and advantages such as mature preparation process are selected as the supporter and the collector of preparation three-diemsnional electrode material at this.The electrode plates of three-dimensional structure provides big reaction interface at three dimensions, thereby reduces the polarization phenomena of interfacial reaction, and then improves the performance of electrode, and with respect to the two-dimensional plane electrode, three-diemsnional electrode can more be given full play to the performance of electrode material.Utilize three-dimensional structure to reduce the interfacial polarization of LiFePO4 in charge and discharge process, can improve its high rate charge-discharge performance effectively, satisfy the requirement of pure electric vehicle and plug-in hybrid electric vehicle the battery fast charging and discharging.
Three-dimensional structure foam metal of the present invention/LiFePO4 one electrode is that (about 100～200nm) LiFePO4 particle is directly grown in the surface of the three-dimensional collector skeleton of foam metal, the electrode plates with 3-D solid structure of formation to nanoscale.This special three-dimensional structure is mainly reflected in the positive role of material property: 1. the foam metal specific area is very big and conductivity is good; It can be formed the conductive network of 3 D stereo as supporter and collector; Increase the electron conduction of material, simultaneously, made the surface area of electrochemical reaction increase greatly; Thereby significantly reduced the interface current density in the electrochemical reaction process, reduced the electrochemical reaction polarization; 2. the special microscopic appearance of three-dimensional porous material, bigger specific area is that lithium ion provides more avtive spot; 3. thin hole wall has reduced the diffusion path of lithium ion effectively, has reduced the ions diffusion resistance; 4. high porosity immerses the electrolysis fluid power effectively, thereby has improved the ionic conducting property of material.5. (about 100～200nm) LiFePO4 particle outside is surrounded by carbon-coating to nanoscale, has restricted the further growth of particle, and has improved the electron conduction of material monolithic.With foam metal/LiFePO4 three-diemsnional electrode material be the lithium ion battery of positive electrode when carrying out high rate charge-discharge, its special three-dimensional structure has guaranteed the high rate performance that lithium ion battery is superior.
The preparation method of three-dimensional structure foam metal of the present invention/LiFePO4 one electrode uses than is easier to the trivalent iron salt for preparing and store as reaction raw materials, compares as raw material with adopting ferrous salt, and cost reduces; Adopt organic molecule carbon source (sucrose and or glucose) raw material; It has three effects in trivalent iron salt is the course of reaction of raw material: 1. the micromolecule carbon source is decomposed the carbon that produces and can be used as ferric reducing agent, makes it be reduced to divalence (iron in the LiFePO4 is divalence); 2. decompose the surface that the carbon that produces can be coated on the LiFePO4 particle, become particle and intergranular space obstacle, limited the size of particle, suppress its undue growth; 3. the carbon-coating of LiFePO4 particle surface has good electron conductivity, improves the conductivity of material to a certain extent, and then has improved the high rate performance of lithium ion battery.The preparation method adopts rheology phase method to prepare composite ferric lithium phosphate material simultaneously; Rheology phase method has sol-gal process concurrently, and (raw materials mix is even, full contact; The preparation sample particle is little and even, but complex process, cycle are long) (technology is simple but sample particle that prepare is bigger, and calcining heat is higher with carbothermic method; Time is longer) advantage, can be under relatively low temperature and short time in prepare that particle is less, the material of even size distribution.
With foam metal of the present invention/LiFePO4 three-diemsnional electrode material is the lithium ion battery of anode pole piece; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 5C charge-discharge magnification, the capability retention of 40 circulation back lithium ion batteries still is higher than 90%; (2) discharge specific discharge capacity: 1C discharge＞110mAhg
-1, 5C discharge＞80mAhg
-1, 10C discharge＞50mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to the LiFePO4 in the three-diemsnional electrode) of active material on the electrode.
Description of drawings
Fig. 1 is that the three-dimensional structure nickel foam/LiFePO4 one electrode of test 1 preparation amplifies 1000 times scanning electron micrograph;
Fig. 2 is that the three-dimensional structure nickel foam/LiFePO4 one electrode of test 1 preparation amplifies 30000 times scanning electron micrograph;
Fig. 3 be with test 1 the preparation three-dimensional structure nickel foam/LiFePO4 one electrode be the charging and discharging curve figure of lithium ion battery under the 0.07C charge-discharge magnification of anode pole piece;
Fig. 4 be with test 1 the preparation three-dimensional structure nickel foam/LiFePO4 one electrode be the high rate performance curve chart of the lithium ion battery of anode pole piece;
Fig. 5 be with test 1 the preparation three-dimensional structure nickel foam/LiFePO4 one electrode be the cycle performance curve chart of lithium ion battery under the 5C charge-discharge magnification of anode pole piece;
Fig. 6 be with test 1 the preparation three-dimensional structure nickel foam/LiFePO4 one electrode be the cyclic voltammetry curve figure of lithium ion battery in 2.5V～3.8V scope of anode pole piece.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: this execution mode is three-dimensional structure foam metal/LiFePO4 one electrode; Three-dimensional structure foam metal/LiFePO4 one electrode is to be supporter and collector with the foam metal, and the nano-grade lithium iron phosphate particle generates and is fixed in that the skeleton surface of foam metal obtains at the foam metal surface in situ; Wherein, foam metal is that the thickness after roll extrusion is handled is the three-dimensional foam metal of 300 μ m～1000 μ m; Described nano-grade lithium iron phosphate particle generates and realize through following operation on the skeleton surface of being fixed in foam metal at the foam metal surface in situ: through trivalent iron salt, P source compound, Li source compound, organic molecule carbon source and deionized water are utilized rheology mutually the rheological body that obtains of method infiltrate to the space of foam metal and obtain three-dimensional precursor; Again with three-dimensional precursor sintering; Realize that the nano-grade lithium iron phosphate particle generates and be fixed in the skeleton surface of foam metal at the foam metal surface in situ; Wherein, Fe in the trivalent iron salt and the mol ratio of the P in the P source compound are 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1, and the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1.
The three-dimensional structure foam metal of this execution mode/LiFePO4 one electrode is that (about 100～200nm) LiFePO4 particle is directly grown in the surface of the three-dimensional collector skeleton of foam metal, the electrode plates with 3-D solid structure of formation to nanoscale.This special three-dimensional structure is mainly reflected in the positive role of material property: 1. the foam metal specific area is very big and conductivity is good; It can be formed the conductive network of 3 D stereo as supporter and collector; Increase the electron conduction of material, simultaneously, made the surface area of electrochemical reaction increase greatly; Thereby significantly reduced the interface current density in the electrochemical reaction process, reduced the electrochemical reaction polarization; 2. the special microscopic appearance of three-dimensional porous material, bigger specific area is that lithium ion provides more avtive spot; 3. thin hole wall has reduced the diffusion path of lithium ion effectively, has reduced the ions diffusion resistance; 4. high porosity immerses the electrolysis fluid power effectively, thereby has improved the ionic conducting property of material.5. (about 100～200nm) LiFePO4 particle outside is surrounded by carbon-coating to nanoscale, has restricted the further growth of particle, and has improved the electron conduction of material monolithic.With foam metal/LiFePO4 three-diemsnional electrode material be the lithium ion battery of positive electrode when carrying out high rate charge-discharge, its special three-dimensional structure has guaranteed the high rate performance that lithium ion battery is superior.
Adopt rheology phase method to be prepared into rheological body in this execution mode; Rheology phase method is a kind of emerging existing method of synthesizing inorganic nonmetallic materials; This method is after solid reactant is mixed according to a certain percentage; Be dissolved in an amount of water or other solvents and form true solution, make liquid viscosity increase through heating or the mode that stirs then, form the rheological body that solids and liquid substance are evenly distributed.In rheological body, the surface energy of solia particle is utilized effectively, and solids contact with liquid substance closely, evenly, and heat exchange is good, is not easy to occur the local overheating phenomenon.Compare with high temperature solid-state synthetic method commonly used, this method has advantages such as synthesis temperature is low, and roasting time is short, and the gained material granule is little and be evenly distributed.Wherein, said rheological body is meant under the effect of stress, produces the object that flows with distortion.
Foam metal/LiFePO4 three-diemsnional electrode material with this execution mode is the lithium ion battery of anode pole piece; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 5C charge-discharge magnification, the capability retention of 40 circulation back lithium ion batteries still is higher than 90%; (2) discharge specific discharge capacity: 1C discharge＞110mAhg
-1, 5C discharge＞80mAhg
-1, 10C discharge＞50mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to the LiFePO4 in the three-diemsnional electrode) of active material on the electrode.
In this execution mode after roll extrusion is handled the thicker of three-dimensional foam metal; The load capacity of nano-grade lithium iron phosphate particle is many more; Then foam metal/LiFePO4 three-diemsnional electrode material is that the surface density of anode pole piece is just big more, can control the thickness of three-dimensional foam metal after roll extrusion is handled according to actual needs.
Embodiment two: this execution mode and embodiment one are different is that described foam metal is that thickness after roll extrusion is handled is the three-dimensional foam metal of 600 μ m～1000 μ m.Other parameter is identical with embodiment one.
Thickness in this execution mode after roll extrusion is handled, 800 μ m～950 μ m preferably, that best is 900 μ m.
When described foam metal is a thickness after roll extrusion is handled when being the three-dimensional foam metal of 900 μ m, foam metal/LiFePO4 three-diemsnional electrode material is that the surface density of LiFePO4 in the anode pole piece is about 100g/m
2
Embodiment three: what this execution mode was different with embodiment one or two is that said foam metal is nickel foam or foamed aluminium.Other step and parameter are identical with embodiment one or two.
The specific area of the foam metal that this execution mode adopts is high; And conductivity is good, and it can be formed the conductive network of 3 D stereo as supporter and collector, has increased the electron conduction of material; Simultaneously; Make the surface area of electrochemical reaction increase greatly, thereby significantly reduced the interface current density in the electrochemical reaction process, reduced the electrochemical reaction polarization; The microscopic appearance that three-dimensional porous material is special, bigger specific area are that lithium ion provides more avtive spot; Thin hole wall has reduced the diffusion path of lithium ion effectively, has reduced the ions diffusion resistance; High porosity immerses the electrolysis fluid power effectively, thereby has improved the ionic conducting property of material.
Embodiment four: what this execution mode and embodiment one, two or three were different is that described trivalent iron salt is ferric nitrate and/or iron chloride; Said P source compound is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate; Said Li source compound is a kind of in lithium nitrate, lithium carbonate and the lithium hydroxide or several kinds of mixtures wherein, and said organic molecule carbon source is sucrose and/or glucose.Other step and parameter are identical with embodiment one, two or three.
When trivalent iron salt was ferric nitrate and iron chloride, both mixed with any ratio in this execution mode.When P source compound was ammonium dihydrogen phosphate and diammonium hydrogen phosphate, both mixed with any ratio.Said Li source compound is during for several kinds of mixtures wherein, with any than mixing.When said organic molecule carbon source was sucrose and glucose, both mixed with any ratio.
Embodiment five: this execution mode is the preparation method like embodiment one described three-dimensional structure foam metal/LiFePO4 one electrode; It is realized through following steps: one, with foam metal carry out roll extrusion handle to thickness be 300 μ m～1000 μ m; Ultrasonic cleaning in alcohol then, dry again; Two, the mol ratio by Fe in the trivalent iron salt and the P in the P source compound is 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing trivalent iron salt, Li source compound, P source compound and organic molecule carbon source; Then with the trivalent iron salt that takes by weighing, Li source compound, P source compound and organic molecule carbon source mix mixture; In mixture, add deionized water again, ultrasonic stirring obtained true solution in 2～4 hours, then true solution was placed to stir under 50～100 ℃ the temperature to form rheological body; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the foam metal after step 1 is handled is immersed in the rheological body that step 2 obtains, foam metal is taken out after being dried to constant weight then, three-dimensional precursor; Four, the three-dimensional precursor that step 3 is obtained places inert gas or reducibility gas special atmosphere oven; Predecomposition is 2～4 hours under 200 ℃～300 ℃ temperature; Be warming up to 550 ℃～650 ℃ then; Insulation calcining 5～12 hours is cooled to room temperature again, gets three-dimensional structure foam metal/LiFePO4 one electrode.
Foam metal is the thickness after roll extrusion is handled in the step 1 of this execution mode, is preferably the three-dimensional foam metal of 600 μ m～1000 μ m, and that more excellent is 800 μ m～950 μ m, and that best is 900 μ m.
The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield in the step 2 of this execution mode is preferably 0.5～0.7: 1, and best is 0.6: 1.
The preparation method of the three-dimensional structure foam metal of this execution mode/LiFePO4 one electrode uses than is easier to the trivalent iron salt for preparing and store as reaction raw materials, compares as raw material with adopting ferrous salt, and cost reduces; Adopt organic molecule carbon source (sucrose and or glucose) raw material; It has three effects in trivalent iron salt is the course of reaction of raw material: 1. the micromolecule carbon source is decomposed the carbon that produces and can be used as ferric reducing agent, makes it be reduced to divalence (iron in the LiFePO4 is divalence); 2. decompose the surface that the carbon that produces can be coated on the LiFePO4 particle, become particle and intergranular space obstacle, limited the size of particle, suppress its undue growth; 3. the carbon-coating of LiFePO4 particle surface has good electron conductivity, improves the conductivity of material to a certain extent, and then has improved the high rate performance of lithium ion battery.The preparation method adopts rheology phase method to prepare composite ferric lithium phosphate material simultaneously; Rheology phase method has sol-gal process concurrently, and (raw materials mix is even, full contact; The preparation sample particle is little and even, but complex process, cycle are long) (technology is simple but sample particle that prepare is bigger, and calcining heat is higher with carbothermic method; Time is longer) advantage, can be under relatively low temperature and short time in prepare that particle is less, the material of even size distribution.
Embodiment six: what this execution mode and embodiment five were different is that foam metal is nickel foam or foamed aluminium in the step 1.Other step and parameter are identical with embodiment five.
The specific area of the foam metal that this execution mode adopts is high; And conductivity is good, and it can be formed the conductive network of 3 D stereo as supporter and collector, has increased the electron conduction of material; Simultaneously; Make the surface area of electrochemical reaction increase greatly, thereby significantly reduced the interface current density in the electrochemical reaction process, reduced the electrochemical reaction polarization; The microscopic appearance that three-dimensional porous material is special, bigger specific area are that lithium ion provides more avtive spot; Thin hole wall has reduced the diffusion path of lithium ion effectively, has reduced the ions diffusion resistance; High porosity immerses the electrolysis fluid power effectively, thereby has improved the ionic conducting property of material.
Embodiment seven: what this execution mode was different with embodiment five or six is that the trivalent iron salt described in the step 2 is ferric nitrate and/or iron chloride; Said P source compound is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate; Said Li source compound is a kind of in lithium nitrate, lithium carbonate and the lithium hydroxide or several kinds of mixtures wherein, and said organic molecule carbon source is sucrose and/or glucose.Other step and parameter and embodiment five or six phase are together.
When trivalent iron salt was ferric nitrate and iron chloride, both mixed with any ratio in this execution mode.When P source compound was ammonium dihydrogen phosphate and diammonium hydrogen phosphate, both mixed with any ratio.Said Li source compound is during for several kinds of mixtures wherein, with any than mixing.When said organic molecule carbon source was sucrose and glucose, both mixed with any ratio.
Embodiment eight: this execution mode and embodiment five, six or seven are different is that foam metal after in the step 3 step 1 being handled is immersed in the rheological body that step 2 obtains; Be after-0.5 MPa, temperature are to be dried to constant weight under 110 ℃ the condition foam metal to be taken out in vacuum degree then, three-dimensional precursor.Other step and parameter are identical with embodiment five, six or seven.
Embodiment nine: what this execution mode was different with one of embodiment five to eight is that the three-dimensional precursor that in the step 4 step 3 is obtained places inert gas or reducibility gas special atmosphere oven; Predecomposition is 2 hours under 260 ℃ temperature; Be warming up to 600 ℃ then, insulation calcining 10 hours.Other step and parameter are identical with one of embodiment five to eight.
Embodiment ten: with embodiment one described three-dimensional structure foam metal/LiFePO4 one electrode is the lithium ion battery of anode pole piece; Comprise positive plate, negative plate, barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in the periphery of positive plate, negative plate and barrier film, and wherein, positive plate is three-dimensional structure foam metal of the present invention/LiFePO4 one electrode.
Plus plate current-collecting body in this execution mode and supporter are foam metal.
Negative plate described in this execution mode is formed by negative current collector and cathode size manufacturing, adopts and well known to a person skilled in the art that negative plate gets final product.For example, cathode size can be by mass percentage be made up of the binding agent Kynoar of the active carbon of 75%～97% graphite type material, 0～15% high-specific surface area and 3%～10% and (be preferably in the cathode size by mass percentage by the active carbon of 80%～90% graphite type material, 5%～12% high-specific surface area and 4%～8% binding agent Kynoar and forms.More preferably be to form by the active carbon of 85% graphite type material, 9% high-specific surface area and 6% binding agent Kynoar by mass percentage), cathode size is evenly distributed on the one side of negative current collector, and the surface density of cathode size is 20～100g/m
2Wherein said graphite type material can be for one or more the mixture in native graphite, Delanium and the carbonaceous mesophase spherules, when graphite type material is mixture, with any than mixing; Said negative current collector can be Copper Foil.When cathode size evenly was coated in the upper and lower surface of plus plate current-collecting body, the twice the when surface density of cathode size is the single face coating was 40～200g/m
2Said conductive agent is a kind of in nano-graphite, acetylene black and the carbon black or several kinds mixture wherein, when conductive agent is mixture, with any than mixing.
In order to verify beneficial effect of the present invention, test as follows:
The test 1: the preparation method of three-dimensional structure nickel foam/LiFePO4 one electrode, it is realized through following steps: one, with nickel foam carry out roll extrusion handle to thickness be 900 μ m, ultrasonic cleaning in alcohol then, again the drying; Two, the mol ratio by Fe in the ferric nitrate and the P in the ammonium dihydrogen phosphate is 1: 1; Li in the lithium nitrate and the mol ratio of the P in the ammonium dihydrogen phosphate are 1～1.1: 1; The mass ratio of sucrose and LiFePO4 theoretical yield is that 0.6: 1 ratio takes by weighing ferric nitrate, lithium nitrate, ammonium dihydrogen phosphate and sucrose, then with the ferric nitrate that takes by weighing, lithium nitrate, ammonium dihydrogen phosphate and sucrose mix mixture, in mixture, add deionized water again; Ultrasonic stirring obtained true solution in 2 hours; Then true solution is placed to stir under 80 ℃ the temperature to form rheological body, wherein, the deionized water quality is 5 times of mixture quality; Three, the nickel foam after step 1 is handled is immersed in the rheological body that step 2 obtains, and be after-0.5 MPa, temperature are to be dried to constant weight under 110 ℃ the condition nickel foam to be taken out in vacuum degree then, must three-dimensional precursor; Four, the three-dimensional precursor that step 3 is obtained places the inert gas shielding atmosphere furnace, and predecomposition is 2 hours under 260 ℃ temperature, is warming up to 600 ℃ then, and insulation calcining 10 hours is cooled to room temperature again, gets three-dimensional structure nickel foam/LiFePO4 one electrode.
The nickel foam that adopts in the test 1 is the commercially available prod.
The three-dimensional structure nickel foam/LiFePO4 one electrode of test 1 preparation is amplified 1000 times of scanning electron micrographs with 30000 times and is distinguished as depicted in figs. 1 and 2; It is thus clear that the nano-grade lithium iron phosphate particle generates and is fixed in the skeleton surface of nickel foam at the nickel foam surface in situ.
Three-dimensional structure nickel foam/LiFePO4 one electrode to test 1 preparation is the lithium ion battery of anode pole piece; Comprise positive plate, negative plate, barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in the periphery of positive plate, negative plate and barrier film, and wherein, positive plate is an anode pole piece for the three-dimensional structure foam metal/LiFePO4 one electrode of test 1 preparation.Wherein, Negative current collector can be Copper Foil in the negative plate; Cathode size is made up of the active carbon of 85% graphite type material, 9% high-specific surface area and 6% binding agent Kynoar by mass percentage; Cathode size is evenly distributed on the one side of negative current collector, and the surface density of cathode size is 60g/m
2Wherein said graphite type material is a native graphite.
With three-dimensional structure nickel foam/LiFePO4 one electrode of testing 1 preparation is that the lithium ion battery of anode pole piece prepares through following steps: one, with resulting three-dimensional structure nickel foam/direct cut-parts of LiFePO4 one electrode, positive plate; Two, take by weighing following cathode size raw material by mass percentage: the active carbon of 85% graphite type material, 9% high-specific surface area and 6% binding agent Kynoar; Three, the negative pole raw material that step 2 is taken by weighing is that-0.5～-0.1 MPa, temperature are under 100～120 ℃ the condition in vacuum degree, vacuumize 6 hours; Four, with the cathode size raw materials mix after the step 3 processing, add dispersant n-formyl sarcolysine base pyrrolidones (NMP) again and stirred 6～8 hours, get cathode size, NMP is 3 times of cathode size raw material binding agent PVDF quality; Five, cathode size evenly is coated on the negative current collector, it is 60gm that control applies single face density
-2(perhaps two-sided density is 120gm
-2), obtain wet negative plate; Six, the wet negative plate drying in vacuum drying chamber that step 5 is obtained obtained negative plate in 4 hours, and wherein drying condition is: vacuum degree-0.5～-0.1 MPa, 100～120 ℃ of baking temperatures.Seven, with the positive plate that obtains and negative plate, barrier film and aluminum-plastic composite membrane assemble soft-package battery; Wherein being infused in the argon gas glove box of electrolyte for lithium ion battery carried out, and promptly accomplishing with three-dimensional structure nickel foam/LiFePO4 one electrode is the preparation method of the lithium ion battery of anode pole piece.
To with three-dimensional structure nickel foam/LiFePO4 one electrode of testing 1 preparation being the lithium ion battery (brief note is a lithium ion battery) of anode pole piece; Carry out the lithium ion battery performance test, method of testing is: charging-discharge tester system is the BTS series high accuracy battery test macro that Shenzhen new Weir company produces, and Experimental cell is 2025 button cells; The charging cut-ff voltage is 3.8V; Discharge cut-off voltage is 2.5V, the battery charging and discharging system be first constant current charge to the cut-ff voltage that charges, constant voltage charge is 30 minutes again; Leave standstill after 5 minutes battery discharge to discharge cut-off voltage, so circulation.The CHI630B electrochemical workstation that the cyclic voltammetric test macro adopts Shanghai occasion China instrument company to produce, with 2025 button cells in 2.5V～3.8V scope with 0.1mVs
-1The speed of sweeping carry out cyclic voltammetry scan test.
The charging and discharging curve of lithium ion battery under the 0.07C charge-discharge magnification that test obtains, as shown in Figure 3, curve 1 is a charging curve among the figure, curve 2 is discharge curves.Visible by Fig. 3, lithium ion battery has bigger specific discharge capacity, discharge capacity＞150mAhg under the 0.07C charge-discharge magnification under little multiplying power
-1
The high rate performance curve of the lithium ion battery that test obtains, as shown in Figure 4, " C " expression discharge-rate among the figure.Visible by Fig. 4, lithium ion battery has superior high rate performance, discharge specific discharge capacity: 1C discharge＞110mAhg
-1, 5C discharge＞80mAhg
-1, 10C discharge＞50mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to the LiFePO4 in the three-diemsnional electrode) of active material on the electrode.
The cycle performance curve of lithium ion battery under the 5C charge-discharge magnification that test obtains, as shown in Figure 5.Visible by Fig. 5, lithium ion battery has superior cycle performance: the capability retention of 40 circulation back lithium ion batteries still is higher than 90%.
The lithium ion battery that obtains of test in 2.5V～3.8V scope with 0.1mVs
-1Sweep the cyclic voltammetry curve that speed scans, as shown in Figure 6.Visible by Fig. 6, lithium ion battery has that the LiFePO 4 material of standard is pairing to go out the peak position.
Claims (10)
1. three-dimensional structure foam metal/LiFePO4 one electrode; It is characterized in that three-dimensional structure foam metal/LiFePO4 one electrode is to be supporter and collector with the foam metal, the nano-grade lithium iron phosphate particle generates and is fixed in that the skeleton surface of foam metal obtains at the foam metal surface in situ; Wherein, foam metal is that the thickness after roll extrusion is handled is the three-dimensional foam metal of 300 μ m～1000 μ m; Described nano-grade lithium iron phosphate particle generates and realize through following operation on the skeleton surface of being fixed in foam metal at the foam metal surface in situ: through trivalent iron salt, P source compound, Li source compound, organic molecule carbon source and deionized water are utilized rheology mutually the rheological body that obtains of method infiltrate to the space of foam metal and obtain three-dimensional precursor; Again with three-dimensional precursor sintering; Realize that the nano-grade lithium iron phosphate particle generates and be fixed in the skeleton surface of foam metal at the foam metal surface in situ; Wherein, Fe in the trivalent iron salt and the mol ratio of the P in the P source compound are 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1, and the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1.
2. three-dimensional structure foam metal according to claim 1/LiFePO4 one electrode is characterized in that described foam metal is that thickness after roll extrusion is handled is the three-dimensional foam metal of 600 μ m～1000 μ m.
3. three-dimensional structure foam metal according to claim 1 and 2/LiFePO4 one electrode is characterized in that said foam metal is nickel foam or foamed aluminium.
4. three-dimensional structure foam metal according to claim 1 and 2/LiFePO4 one electrode; It is characterized in that described trivalent iron salt is ferric nitrate and/or iron chloride; Said P source compound is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate; Said Li source compound is a kind of in lithium nitrate, lithium carbonate and the lithium hydroxide or several kinds of mixtures wherein, and said organic molecule carbon source is sucrose and/or glucose.
5. the preparation method of three-dimensional structure foam metal as claimed in claim 1/LiFePO4 one electrode; The preparation method who it is characterized in that three-dimensional structure foam metal/LiFePO4 one electrode realizes through following steps: one, with foam metal carry out roll extrusion handle to thickness be 300 μ m～1000 μ m; Ultrasonic cleaning in alcohol then, dry again; Two, the mol ratio by Fe in the trivalent iron salt and the P in the P source compound is 1: 1; Li in the Li source compound and the mol ratio of the P in the P source compound are 1～1.1: 1; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing trivalent iron salt, Li source compound, P source compound and organic molecule carbon source; Then with the trivalent iron salt that takes by weighing, Li source compound, P source compound and organic molecule carbon source mix mixture; In mixture, add deionized water again, ultrasonic stirring obtained true solution in 2～4 hours, then true solution was placed to stir under 50～100 ℃ the temperature to form rheological body; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the foam metal after step 1 is handled is immersed in the rheological body that step 2 obtains, foam metal is taken out after being dried to constant weight then, three-dimensional precursor; Four, the three-dimensional precursor that step 3 is obtained places inert gas or reducibility gas special atmosphere oven; Predecomposition is 2～4 hours under 200 ℃～300 ℃ temperature; Be warming up to 550 ℃～650 ℃ then; Insulation calcining 5～12 hours is cooled to room temperature again, gets three-dimensional structure foam metal/LiFePO4 one electrode.
6. the preparation method of three-dimensional structure foam metal according to claim 5/LiFePO4 one electrode is characterized in that foam metal is nickel foam or foamed aluminium in the step 1.
7. according to the preparation method of claim 5 or 6 described three-dimensional structure foam metal/LiFePO4 one electrodes; It is characterized in that the trivalent iron salt described in the step 2 is ferric nitrate and/or iron chloride; Said P source compound is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate; Said Li source compound is a kind of in lithium nitrate, lithium carbonate and the lithium hydroxide or several kinds of mixtures wherein, and said organic molecule carbon source is sucrose and/or glucose.
8. according to the preparation method of claim 5 or 6 described three-dimensional structure foam metal/LiFePO4 one electrodes; Foam metal after it is characterized in that in the step 3 step 1 handled is immersed in the rheological body that step 2 obtains; Be after-0.5 MPa, temperature are to be dried to constant weight under 110 ℃ the condition foam metal to be taken out in vacuum degree then, three-dimensional precursor.
9. according to the preparation method of claim 5 or 6 described three-dimensional structure foam metal/LiFePO4 one electrodes; It is characterized in that the three-dimensional precursor that in the step 4 step 3 is obtained places inert gas or reducibility gas special atmosphere oven; Predecomposition is 2 hours under 260 ℃ temperature; Be warming up to 600 ℃ then, insulation calcining 10 hours.
10. be the lithium ion battery of anode pole piece with three-dimensional structure foam metal as claimed in claim 1/LiFePO4 one electrode; Comprise positive plate, negative plate, barrier film and aluminum-plastic composite membrane; Said barrier film is between positive plate and negative plate; Aluminum-plastic composite membrane is wrapped in the periphery of positive plate, negative plate and barrier film, it is characterized in that positive plate is three-dimensional structure foam metal/LiFePO4 one electrode.
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