CN102306783A - Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material - Google Patents
Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material Download PDFInfo
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- iron phosphate
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- lithium iron
- positive electrode
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 90
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract 27
- 239000010405 anode material Substances 0.000 title 1
- 238000009830 intercalation Methods 0.000 claims abstract description 57
- 230000002687 intercalation Effects 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 239000002033 PVDF binder Substances 0.000 claims abstract description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract 8
- 239000011574 phosphorus Substances 0.000 claims abstract 8
- 150000003839 salts Chemical class 0.000 claims abstract 8
- 150000003384 small molecules Chemical class 0.000 claims abstract 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000011267 electrode slurry Substances 0.000 claims abstract 6
- 239000000203 mixture Substances 0.000 claims description 34
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 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 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 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 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 125000000185 sucrose group Chemical group 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 2
- 238000000354 decomposition reaction Methods 0.000 claims 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 35
- 239000002245 particle Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 69
- 229910052493 LiFePO4 Inorganic materials 0.000 description 65
- 239000003795 chemical substances by application Substances 0.000 description 21
- 238000004513 sizing Methods 0.000 description 21
- 238000005303 weighing Methods 0.000 description 15
- 150000002505 iron Chemical class 0.000 description 13
- 239000011229 interlayer Substances 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 10
- 238000003487 electrochemical reaction Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 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 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000000518 rheometry Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003860 storage 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
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003786 synthesis reaction 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
- 229910052786 argon 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
多层石墨烯/磷酸铁锂插层复合材料、其制备方法及以其为正极材料的锂离子电池，涉及磷酸铁锂复合材料、制备方法及以其为正极材料的锂离子电池，解决现有磷酸铁锂材料电子导电性差、以其为正极材料的锂离子电池大倍率充放电性能差的问题，提高动力锂离子电池快速充电能力，满足纯电动车要求。复合材料是将多层石墨烯、三价铁盐、磷源化合物、锂源化合物和有机小分子碳源采用流变相法得复合前驱体，再烧结即可。锂离子电池正极片的正极浆料由复合材料、导电剂和聚偏氟乙烯组成。复合材料为磷酸铁锂颗粒穿插于多层石墨烯的层间的夹层结构；三价铁盐为原料，成本降低；锂离子电池充放电循环性能好，20C倍率下质量比容量大于60mA·h·g-1。
Multilayer graphene/lithium iron phosphate intercalation composite material, its preparation method and lithium ion battery using it as positive electrode material, relates to lithium iron phosphate composite material, preparation method and lithium ion battery using it as positive electrode material, solving existing Lithium iron phosphate material has poor electronic conductivity, and the high-rate charge-discharge performance of lithium-ion batteries using it as the positive electrode material is poor. Improve the fast charging capability of power lithium-ion batteries to meet the requirements of pure electric vehicles. The composite material is a composite precursor obtained by rheological phase method of multilayer graphene, ferric salt, phosphorus source compound, lithium source compound and organic small molecule carbon source, and then sintered. The positive electrode slurry of the lithium ion battery positive plate is composed of composite material, conductive agent and polyvinylidene fluoride. The composite material is a sandwich structure in which lithium iron phosphate particles are interspersed between layers of multi-layer graphene; ferric salt is used as a raw material, and the cost is reduced; the lithium-ion battery has good charge-discharge cycle performance, and the mass specific capacity is greater than 60mA h at 20C rate g -1 .
Description
Technical field
The present invention relates to a kind of composite ferric lithium phosphate material, preparation method and be the lithium ion battery of positive electrode with it.
Background technology
It is good that ferric phosphate lithium cell has a fail safe, has extended cycle life, and advantages of environment protection is the ideal source system that drives electric automobile.But present ferric phosphate lithium cell also is difficult to satisfy pure electric vehicle and plug-in hybrid electric vehicle to the requirement of quickly charging battery aspect high rate capability, restricted the development of ev industry.
The rare good conductivity of graphite; Specific area is big; Has outstanding super capacitor character; If can utilize the rare nanometer laminated structure of multilayer graphite; LiFePO 4 material is compound to the rare interlayer of multilayer graphite; Prepare multi-layer graphene/LiFePO4 intercalation composite material and as the hybrid energy-storing battery of positive electrode; The super capacitor character that graphite is rare when the battery fast charging and discharging can be shared electric current; Make the hybrid energy-storing battery not only have high-energy-density but also have high power density, can satisfy the requirement of pure electric vehicle and plug-in hybrid electric vehicle quickly charging battery.
Summary of the invention
The objective of the invention is in order to solve existing LiFePO 4 material poorly conductive; With it is the problem of the lithium ion battery high rate charge-discharge poor performance of positive electrode, the invention provides a kind of multi-layer graphene/LiFePO4 intercalation composite material, its preparation method and is the lithium ion battery of positive electrode with it.
Multi-layer graphene of the present invention/LiFePO4 intercalation composite material; Be through with multi-layer graphene; Trivalent iron salt; P source compound; Li source compound and organic molecule carbon source adopt rheology mutually legal system get composite precursor; Again the composite precursor sintering is obtained; 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; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1, and the mass ratio of multi-layer graphene and LiFePO4 theoretical yield is 0.005～0.3: 1.
The preparation method of multi-layer graphene of the present invention/LiFePO4 intercalation composite material; Realize through following steps: one, the mol ratio in Fe, P and Li is Fe: P: Li=1: 1: 1～11 ratio takes by weighing trivalent iron salt, P source compound and Li source compound; In the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing the organic molecule carbon source, is that 0.005～0.3: 1 ratio takes by weighing multi-layer graphene in the mass ratio of multi-layer graphene and LiFePO4 theoretical yield; Two, the trivalent iron salt that step 1 is taken by weighing, P source compound, Li source compound, organic molecule carbon source and multi-layer graphene mix mixture; In mixture, add deionized water then; Ultrasonic stirring obtained dispersion liquid in 2～4 hours again; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the dispersion liquid that step 2 is obtained places and stirs the rheological body that makes generation under 50～100 ℃ the temperature and be immersed in the rare interlayer of multilayer graphite and form intercalated compound, then intercalated compound is dried to constant weight and makes composite precursor; Four, the composite precursor that step 3 is obtained grind powder, then powder is placed the special atmosphere oven predecomposition of inert gas and/or reducibility gas to get intermediate product, control predecomposition temperature is 200～300 ℃, the predecomposition time is 2～4 hours; Five, the intermediate product that step 4 is obtained places the special atmosphere oven of inert gas and/or reducibility gas to calcine, and is cooled to room temperature then and obtains calcined product, and wherein, calcining heat is 550～650 ℃, and calcination time is 5～12 hours; Six, the calcined product of step 5 is pulverized sorting, promptly get multi-layer graphene/LiFePO4 intercalation composite material.
Rheological body described in the step 3 of the present invention is meant under the effect of stress, produces the object that flows with distortion.The rheological body that forms in this execution mode requires to have solids and is evenly distributed with liquid substance, contacts closely, the characteristics that heat exchange is good.
The present invention is the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material; 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 positive plate; The periphery of negative plate and barrier film; Wherein, Positive plate is formed by plus plate current-collecting body and anode sizing agent manufacturing; Said anode sizing agent is by mass percentage by multi-layer graphene/LiFePO4 intercalation composite material of 80%～95%; 2%～10% conductive agent and 3%～10% binding agent Kynoar are formed, and the coated face density of anode sizing agent in the anode collection surface is 50～200g/m
2
The interlayer that is interspersed in multi-layer graphene for the LiFePO4 of minimum particle diameter (being lower than 10nm) in multi-layer graphene of the present invention/LiFePO4 intercalation composite material forms sandwich.This special construction is mainly reflected in the positive role of material property: 1. the multi-layer graphene specific area is very big and conductivity is good; Add the conductive network that just can in material, form 3 D stereo on a small quantity; 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; 2. the multi-layer graphene that is adopted is the dough with layer structure, interlamellar spacing big (about 7～8nm), can form small LiFePO4 particle at interlayer, the ions diffusion approach has been shortened in the growth of limiting material particle diameter, reduces the ions diffusion resistance; 3. the LiFePO4 that does not get into interlayer may have grown into larger particles (about 100nm), and the particle outside is surrounded by carbon-coating, has restricted the further growth of particle, has improved the electron conduction of material monolithic.4. the bigger serface of multi-layer graphene can make it in the extremely short time, realize the storage and the release of a large amount of electric charges, has super capacitor character.With multi-layer graphene/LiFePO4 intercalation composite material be the lithium ion battery of positive electrode when carrying out high rate charge-discharge, the multi-layer graphene material very first time is realized capability response, thereby has guaranteed the high rate performance that lithium ion battery is superior.
The preparation method of multi-layer graphene of the present invention/LiFePO4 intercalation composite material 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; (the C number is 5～15 organic carbon source to adopt the organic molecule carbon source; Like sucrose, 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 with carbothermic method; Calcining heat is higher; 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 multi-layer graphene of the present invention/LiFePO4 intercalation composite material is the lithium ion battery of positive electrode; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 10C charge-discharge magnification, the capability retention of 70 circulation back lithium ion batteries still is higher than 95%; (2) discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode; (3) rapid charge characteristic: earlier with the 1C constant-current discharge to 2.5V; Again with the 20C constant current charge to 4.2V; Constant voltage charge then, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Description of drawings
Fig. 1 be embodiment ten the charging and discharging curve of lithium ion battery under the 0.2C charge-discharge magnification, curve 1 is a charging curve, curve 2 is discharge curves; Fig. 2 is the high rate performance curve of the lithium ion battery of embodiment ten; Fig. 3 is the cycle performance curve of lithium ion battery under the 10C charge-discharge magnification of embodiment ten; Fig. 4 be embodiment ten lithium ion battery formerly with the 1C constant-current discharge to 2.5V, again with the 20C constant current charge to 4.2V, the rapid charge characteristic curve in the charge and discharge mode of constant voltage charge then.
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 multi-layer graphene/LiFePO4 intercalation composite material; It is through with multi-layer graphene; Trivalent iron salt; P source compound; Li source compound and organic molecule carbon source adopt rheology mutually legal system get composite precursor; Again the composite precursor sintering is obtained; 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; The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.4～0.8: 1, and the mass ratio of multi-layer graphene and LiFePO4 theoretical yield is 0.005～0.3: 1.
The sandwich of multi-layer graphene in this execution mode/LiFePO4 intercalation composite material is mainly reflected in the positive role that material property promotes: 1. the multi-layer graphene specific area is very big and conductivity is good; Add the conductive network that just can in material, form 3 D stereo on a small quantity; 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; 2. the multi-layer graphene that is adopted is the dough with layer structure, interlamellar spacing big (about 7～8nm), can form small LiFePO4 particle at interlayer, the ions diffusion approach has been shortened in the growth of limiting material particle diameter, reduces the ions diffusion resistance; 3. the LiFePO4 that does not get into interlayer may have grown into larger particles (about 100nm), and the particle outside is surrounded by carbon-coating, has restricted the further growth of particle, has improved the electron conduction of material monolithic.4. the bigger serface of multi-layer graphene can make it in the extremely short time, realize the storage and the release of a large amount of electric charges.With multi-layer graphene/LiFePO4 intercalation composite material be the lithium ion battery of positive electrode when carrying out high rate charge-discharge, the multi-layer graphene material very first time is realized capability response, thereby has guaranteed the high rate performance that lithium ion battery is superior.
Multi-layer graphene/LiFePO4 intercalation composite material with this execution mode is the lithium ion battery of positive electrode; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 10C charge-discharge magnification, the capability retention of 70 circulation back lithium ion batteries still is higher than 95%; (2) discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode; (3) rapid charge characteristic: earlier with the 1C constant-current discharge to 2.5V; Again with the 20C constant current charge to 4.2V; Constant voltage charge then, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Embodiment two: what this execution mode and embodiment one were different is that said trivalent iron salt is ferric nitrate or iron chloride; Said P source compound is ammonium dihydrogen phosphate or ammonium hydrogen phosphate; Said Li source compound is a kind of or wherein several mixture in lithium nitrate, lithium carbonate and the lithium hydroxide, and said organic molecule carbon source is sucrose and/or glucose.Other parameter is identical with embodiment one.
When Li source compound is mixture, mix in this execution mode with any ratio.When organic micromolecule carbon source is two kinds mixture, with sucrose C
12H
22O
11With glucose C
6H
12O
6Mol ratio be 1: 2～4 mixed.
Embodiment three: this execution mode is different with embodiment one or two is that the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is 0.5～0.7: 1.Other parameter is identical with embodiment one or two.
What the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield was best in this execution mode is 0.6: 1.
Embodiment four: this execution mode and embodiment one, two or three are different is that the mass ratio of multi-layer graphene and LiFePO4 theoretical yield is 0.008～0.2: 1.Other parameter is identical with embodiment one, two or three.
The mass ratio of multi-layer graphene and LiFePO4 theoretical yield is preferably 0.01～0.1 in this execution mode, optimally is 0.05: 1.
Embodiment five: this execution mode is the preparation method of multi-layer graphene/LiFePO4 intercalation composite material; It is realized through following steps: one, the mol ratio in Fe, P and Li is Fe: P: Li=1: 1: 1～1.1 ratio takes by weighing trivalent iron salt, P source compound and Li source compound; In the mass ratio of organic molecule carbon source and LiFePO4 theoretical yield is that 0.4～0.8: 1 ratio takes by weighing the organic molecule carbon source, is that 0.005～0.3: 1 ratio takes by weighing multi-layer graphene in the mass ratio of multi-layer graphene and LiFePO4 theoretical yield; Two, the trivalent iron salt that step 1 is taken by weighing, P source compound, Li source compound, organic molecule carbon source and multi-layer graphene mix mixture; In mixture, add deionized water then; Ultrasonic stirring obtained dispersion liquid in 2～4 hours again; Wherein, the deionized water quality is 5～10 times of mixture quality; Three, the dispersion liquid that step 2 is obtained places and stirs the rheological body that makes generation under 50～100 ℃ the temperature and be immersed in the rare interlayer of multilayer graphite and form intercalated compound, then intercalated compound is dried to constant weight and makes composite precursor; Four, the composite precursor that step 3 is obtained grind powder, then powder is placed the special atmosphere oven predecomposition of inert gas and/or reducibility gas to get intermediate product, control predecomposition temperature is 200～300 ℃, the predecomposition time is 2～4 hours; Five, the intermediate product that step 4 is obtained places the special atmosphere oven of inert gas and/or reducibility gas to calcine, and is cooled to room temperature then and obtains calcined product, and wherein, calcining heat is 550～650 ℃, and calcination time is 5～12 hours; Six, the calcined product of step 5 is pulverized sorting, promptly get multi-layer graphene/LiFePO4 intercalation composite material.
The multi-layer graphene that this execution mode obtains/LiFePO4 intercalation composite material is the interlayer formation sandwich that the LiFePO4 of minimum particle diameter (being lower than 10nm) is interspersed in multi-layer graphene.Adopt than the trivalent iron salt that is easier to prepare and stores as reaction raw materials, it is compared as raw material with the use ferrous salt, and cost is lower.
Rheology in this execution mode step 2 and step 3 method mutually is a kind of new 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; Mode through heating or stirring makes liquid viscosity increase then; The rheological body that formation solids and liquid substance are evenly distributed (is that rheological body described in the step 3 is meant under the effect of stress, produces the object that flows with distortion.The rheological body that forms in this execution mode requires to have solids and is evenly distributed with liquid substance, contacts closely, the characteristics that heat exchange is good).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 synthesis 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.
The multi-layer graphene specific area that adopts in this execution mode is very big and conductivity is good; Add the conductive network that just can in material, form 3 D stereo on a small quantity; Increased the electron conduction of material; 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; Interlamellar spacing big (about 7～8nm), can form small LiFePO4 particle at interlayer, the ions diffusion approach has been shortened in the growth of limiting material particle diameter, reduces the ions diffusion resistance; Its bigger specific area can realize the storage and the release of a large amount of electric charges in the extremely short time.The objective of the invention is to by adopting the adding of rheology phase method synthesis technique and multi-layer graphene; Make the multi-layer graphene/LiFePO4 intercalation composite material that obtains possess special intercalation configuration; And the large current density electrical feature that possesses electric chemical super capacitor; Thereby the lithium ion battery that this Composite Preparation of application is gone out not only can utilize the characteristic of multi-layer graphene material fast charging and discharging; Increase the electrochemical reaction surface area of LiFePO 4 material simultaneously and shortened lithium ion diffusion path; Reduced the interfacial reaction polarization of this material in charge and discharge process, the comprehensive function of the two has significantly improved the high rate charge-discharge performance of lithium ion battery.
The mass ratio of organic molecule carbon source and LiFePO4 theoretical yield preferably is 0.5～0.7: 1 in this execution mode step 1, and best is 0.6: 1.
The mass ratio of multi-layer graphene and LiFePO4 theoretical yield preferably is 0.005～0.3: 1 in the step 1, is 0.008～0.2 better, more preferably is 0.01～0.1, optimally is 0.05: 1.
Be that-0.5 MPa, temperature are to be dried to constant weight under 110 ℃ the condition to make composite precursor with intercalated compound in vacuum degree in the step 3.
In the step 4 more preferably be, control predecomposition temperature is 260 ℃, and the predecomposition time is 2 hours.
In the step 5 more preferably be, calcining heat is 600 ℃, and calcination time is 10 hours.
In the step 6, carry out sorting after adopting 400 mesh sieves that the calcined product of step 5 is pulverized.
Embodiment six: what this execution mode and embodiment five were different is that trivalent iron salt described in the step 1 is ferric nitrate or iron chloride; Said P source compound is ammonium dihydrogen phosphate or ammonium hydrogen phosphate; Said Li source compound is a kind of or wherein several mixture in lithium nitrate, lithium carbonate and the lithium hydroxide, and said organic molecule carbon source is sucrose and/or glucose.Other parameter is identical with embodiment five.
When Li source compound is mixture, mix in this execution mode with any ratio.When organic micromolecule carbon source is two kinds mixture, with sucrose C
12H
22O
11With glucose C
6H
12O
6Mol ratio be 1: 2～4 mixed.
Embodiment seven: this execution mode is the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material; 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 positive plate; The periphery of negative plate and barrier film; Wherein, Positive plate is formed by plus plate current-collecting body and anode sizing agent manufacturing; Said anode sizing agent is by mass percentage by multi-layer graphene/LiFePO4 intercalation composite material of 80%～95%; 2%～10% conductive agent and 3%～10% binding agent Kynoar are formed, and the coated face density of anode sizing agent in the anode collection surface is 50～200g/m
2
This execution mode be the lithium ion battery of positive electrode with multi-layer graphene/LiFePO4 intercalation composite material; Have following performance: the high rate charge-discharge cycle performance that (1) is good: under the 10C charge-discharge magnification, the capability retention of 70 circulation back lithium ion batteries still is higher than 95%; (2) discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode; (3) rapid charge characteristic: earlier with the 1C constant-current discharge to 2.5V; Again with the 20C constant current charge to 4.2V; Constant voltage charge then, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Anode sizing agent is single face coating in the anode collection surface in this execution mode, anode sizing agent the coated face density of anode collection surface preferable be 80～150g/m
2, that more excellent is 100g/m
2
And when anode sizing agent evenly was coated in the upper and lower surface of plus plate current-collecting body, the twice the when surface density of anode sizing agent is the single face coating was 100～400g/m
2
Plus plate current-collecting body in this execution mode is an aluminium foil.
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
2
Embodiment eight: what this execution mode and embodiment seven were different is that said conductive agent is a kind of or wherein several mixture in nano-graphite, acetylene black and the carbon black.Other parameter is identical with embodiment seven.
When conductive agent is mixture, mix in this execution mode with any ratio.
Embodiment nine: this execution mode is different with embodiment seven or eight is that said anode sizing agent is made up of multi-layer graphene/LiFePO4 intercalation composite material of 80%～90%, 5%～10% conductive agent and 5%～10% binding agent Kynoar by mass percentage.Other parameter is identical with embodiment seven or eight.
Embodiment ten: this execution mode is different with embodiment seven or eight is that said anode sizing agent is made up of multi-layer graphene/LiFePO4 intercalation composite material of 80%, 10% conductive agent and 10% binding agent Kynoar by mass percentage, and the coated face density of anode sizing agent in the anode collection surface is 100g/m
2Other parameter is identical with embodiment seven or eight.
Conductive agent described in this execution mode is a nano-graphite.
Multi-layer graphene described in this execution mode/LiFePO4 intercalation composite material; Realize through following steps: one, the mol ratio in Fe, P and Li is Fe: P: Li=1: 1: 1.05 ratio takes by weighing ferric nitrate, ammonium dihydrogen phosphate and lithium nitrate; In the mass ratio of sucrose and LiFePO4 theoretical yield is that 0.6: 1 ratio takes by weighing sucrose, is that 0.05: 1 ratio takes by weighing multi-layer graphene in the mass ratio of multi-layer graphene and LiFePO4 theoretical yield; Two, the ferric nitrate that step 1 is taken by weighing, ammonium dihydrogen phosphate, lithium nitrate, sucrose and multi-layer graphene mix mixture; In mixture, add deionized water then; Obtained dispersion liquid in 2 hours 40 ℃ of following ultrasonic stirring again, wherein, the deionized water quality is 5 times of mixture quality; Three, the dispersion liquid that step 2 is obtained places and stirs the rheological body that makes generation under 80 ℃ the temperature and be immersed in the rare interlayer of multilayer graphite and form intercalated compound; Be-0.5 MPa with intercalated compound in vacuum degree then, baking temperature is to be dried to constant weight under 110 ℃ the condition to make composite precursor; Four, the composite precursor that step 3 is obtained grinds 5min and gets powder, then powder is placed the tube furnace predecomposition of the protective atmosphere of inert gas to get intermediate product, and control predecomposition temperature is 260 ℃, and the predecomposition time is 2 hours; Five, the intermediate product that step 4 is obtained places the tube furnace of the protective atmosphere of inert gas to calcine, and is cooled to room temperature then and obtains calcined product, and wherein, calcining heat is 600 ℃, and calcination time is 10 hours; Six, after the calcined product pulverizing with step 5, cross 400 mesh sieves and carry out sorting, promptly get multi-layer graphene/LiFePO4 intercalation composite material.Wherein, multi-layer graphene is the commercially available prod.
The cathode size of this execution mode 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; Said negative current collector can be Copper Foil.
This execution mode be that the lithium ion battery of positive electrode prepares through following steps with multi-layer graphene/LiFePO4 intercalation composite material: one, take by weighing following anode sizing agent raw material by mass percentage: 80% multi-layer graphene/LiFePO4 intercalation composite material, 10% acetylene black conductive agent and 10% binding agent Kynoar (PVDF) are formed, and then 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; Two, anodal raw material that step 1 is taken by weighing and negative pole raw material are that-0.5～-0.1 MPa, temperature are under 100～120 ℃ the condition in vacuum degree respectively, vacuumize 6 hours; Three, with the anode sizing agent raw materials mix after the step 2 processing; Adding dispersant n-formyl sarcolysine base pyrrolidones (NMP) again stirred 6～8 hours; Get anode sizing agent; NMP is 3 times of anode sizing agent raw material binding agent PVDF quality, and then will the cathode size raw materials mix after step 2 is handled stirs and promptly get cathode size; Four, anode sizing agent evenly is coated on the plus plate current-collecting body, it is 100gm that control applies single face density
-2(perhaps two-sided density is 200gm
-2), obtain wet positive plate, again 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; Five, wet positive plate that step 4 is obtained and wet negative plate drying in vacuum drying chamber obtained positive plate and negative plate in 4 hours, and wherein drying condition is: vacuum degree-0.5～-0.1 MPa, 100～120 ℃ of baking temperatures.Six, step 5 is obtained positive plate 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 multi-layer graphene/LiFePO4 intercalation composite material is the preparation method of the lithium ion battery of positive electrode.
As a comparison; Carry out following contrast experiment: lithium ion battery; 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; Wherein, Positive plate is formed by plus plate current-collecting body aluminium foil and anode sizing agent manufacturing; Said anode sizing agent is made up of 80% LiFePO4,10% acetylene black conductive agent and 10% binding agent Kynoar by mass percentage, and the coated face density of anode sizing agent in the anode collection surface is 100g/m
2Wherein, LiFePO4 is existing commercially available prod.Negative plate is the same with negative plate in the embodiment ten.Its preparation method be that the preparation method of lithium ion battery of positive electrode is consistent with multi-layer graphene/LiFePO4 intercalation composite material described in the embodiment ten, different is to adopt LiFePO4 to replace multi-layer graphene/LiFePO4 intercalation composite material.
The lithium ion battery that lithium ion battery that embodiment ten is obtained and contrast experiment obtain; Carry out battery performance test respectively; Method of testing is: charging-discharge tester system is the BTS series high accuracy battery test macro that Shenzhen new Weir company produces; Experimental cell is 2025 button cells; The charging cut-ff voltage is 4.2V; Discharge cut-off voltage is 2.5V; The battery charging and discharging system is that first constant current charge is to the cut-ff voltage that charges; Constant voltage charge a period of time again; Battery discharge is to discharge cut-off voltage after leaving standstill a period of time, a loop ends.
The charging and discharging curve of lithium ion battery under the 0.2C charge-discharge magnification of the embodiment ten that test obtains, as shown in Figure 1, curve 1 is a charging curve among the figure, curve 2 is discharge curves.Visible by Fig. 1, the lithium ion battery of embodiment ten has bigger specific discharge capacity, discharge capacity＞150mAhg under the 0.2C charge-discharge magnification under little multiplying power
-1
The high rate performance curve of the lithium ion battery of the embodiment ten that test obtains, as shown in Figure 2, " C " expression discharge-rate among the figure.Visible by Fig. 2, the lithium ion battery of embodiment ten has superior high rate performance, discharge specific discharge capacity: 1C discharge＞140mAhg
-1, 5C discharge＞120mAhg
-1, 10C discharge＞110mAhg
-1, 20C discharge＞100mAhg
-1, wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode.
The cycle performance curve of lithium ion battery under the 10C charge-discharge magnification of the embodiment ten that test obtains, as shown in Figure 3.Visible by Fig. 3, the lithium ion battery of embodiment ten has superior cycle performance: the capability retention of 70 circulation back lithium ion batteries still is higher than 95%.
The lithium ion battery of the embodiment ten that obtains of test formerly with the 1C constant-current discharge to 2.5V, again with the 20C constant current charge to 4.2V, the rapid charge characteristic curve in the charge and discharge mode of constant voltage charge then, as shown in Figure 4.Visible by Fig. 4, the lithium ion battery of embodiment ten has the superior performance of filling soon, can be charged in 200 seconds 95%, 400 second of total capacity can be charged to total capacity 98% (the charging specific discharge capacity of positive active material under this system is 150mAhg
-1).
Test the lithium ion battery of embodiment ten and lithium ion battery specific discharge capacity under different discharge-rates of contrast experiment simultaneously, as shown in table 1.
Table 1 is the lithium ion battery of embodiment ten and lithium ion battery specific discharge capacity under different discharge-rates of contrast experiment.Wherein, the discharge specific discharge capacity is meant the specific discharge capacity of (referring to multi-layer graphene/LiFePO4 intercalation composite material) of active material on the electrode.
Table 1
It is thus clear that the lithium ion battery of concrete mode ten has well big multiplying power specific discharge capacity, the high rate charge-discharge performance is good.The rated voltage of the lithium ion battery that practical implementation ten obtains is 3.2V.
Claims (10)
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