CN117410579B - Preparation method and application of high-performance lithium ion battery for energy storage - Google Patents
Preparation method and application of high-performance lithium ion battery for energy storage Download PDFInfo
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- CN117410579B CN117410579B CN202311719228.1A CN202311719228A CN117410579B CN 117410579 B CN117410579 B CN 117410579B CN 202311719228 A CN202311719228 A CN 202311719228A CN 117410579 B CN117410579 B CN 117410579B
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- graphene oxide
- iron phosphate
- lithium iron
- positive plate
- lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000004146 energy storage Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 178
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 176
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 123
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 238000001035 drying Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 12
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 238000004080 punching Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 49
- 239000003792 electrolyte Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000011267 electrode slurry Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000011246 composite particle Substances 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 19
- 238000005056 compaction Methods 0.000 abstract description 16
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000003273 ketjen black Substances 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- -1 EDTA-2 Na) solution Chemical compound 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- JAVMESYEMAASLS-UHFFFAOYSA-N tetraazanium dihydrogen phosphate phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].OP(O)([O-])=O.[O-]P([O-])([O-])=O JAVMESYEMAASLS-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 102220479740 Cell division cycle protein 123 homolog_S11I_mutation Human genes 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The preparation method of the high-performance lithium ion battery for energy storage and the application thereof, wherein the preparation method of the positive plate comprises the following steps: s1, pulping; wherein the reduced graphene oxide/lithium iron phosphate composite material is a flaky lithium iron phosphate nanoparticle in-situ grown on the surface of the reduced graphene oxide; s2, coating; s3, drying; s4, extruding the positive plate until the compaction density is 2.4g/cm 3 ～2.7g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the inorganic filler is nano particles, and the extruded Cheng Haiyuan graphene oxide/lithium iron phosphate composite material moves in the positive plate; s5, punching and drying to obtain the positive plate. According to the invention, the iron source is chelated and positioned by utilizing graphene oxide and disodium ethylenediamine tetraacetate, so that the uniform position relationship between the graphene oxide and the generated lithium iron phosphate is effectively ensured, the sheet lithium iron phosphate loaded by the reduced graphene oxide is prepared, and the compaction density of the obtained positive plate is promoted by matching with inorganic filler particles and extrusion.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method and application of a high-performance lithium ion battery for energy storage.
Background
The lithium iron phosphate has low electric conductivity and belongs to semiconductor materials. LiFePO of olivine structure 4 In Li + During the deintercalation process, mixed valence cations (Fe 3+ /Fe 2+ ) Therefore, the method can be used for manufacturing the optical fiber,the electron conductivity is significantly lower.
In olivine LiFePO 4 In the crystal structure, O is distributed in quasi-hexagonal close packing, leading to Li + Shared in forming edges [ LiO 6 ]In the case of octahedron, only the edges [010 ]]The direction realizes one-dimensional diffusion. At the same time, at [ FeO ] 6 ]And [ LiO ] 6 ][ PO between two types of octahedra 4 ]Tetrahedra, to a great extent limit LiFePO 4 Is a change in volume of Li during charge and discharge + Quickly insert and remove. LiFePO 4 Li with crystal structure + One-dimensional diffusion mode leading to Li + Is very low, severely hampering Li + The diffusion of (c) causes a problem of localized "dead lithium", thereby reducing the amount of active material involved in the reaction of the battery, and the cycle performance and capacity of the battery are reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method and application of a high-performance lithium ion battery for energy storage, which can improve the compaction density of a positive plate of the lithium ion battery and improve the electronic conductivity and the ionic conductivity of a material.
According to the invention, the iron source is chelated and positioned by utilizing graphene oxide and disodium ethylenediamine tetraacetate, so that the uniform position relationship between the graphene oxide and the generated lithium iron phosphate is effectively ensured, the electronic conductivity and the ionic conductivity of the material are improved, and the compaction density of the positive plate can be effectively improved by preparing the flaky lithium iron phosphate loaded by the reduced graphene oxide.
In order to solve the technical problem, the technical scheme of the invention is as follows: the preparation method of the high-performance lithium ion battery for energy storage comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the preparation method of the positive plate comprises the following steps:
s1, pulping;
mixing a reduced graphene oxide/lithium iron phosphate composite material (in the form of particles), a conductive agent, a binder, a dispersing agent and an inorganic filler, uniformly stirring, and dissolving the mixture in a solvent for dispersion to obtain anode slurry; wherein the reduced graphene oxide/lithium iron phosphate composite material is a flaky lithium iron phosphate nanoparticle in-situ grown on the surface of the reduced graphene oxide;
in step S1, the selection of the conductive agent, the binder, and the dispersant is all in the prior art. In the "dispersing by dissolving it in a solvent", deionized water is preferable for the solvent to be dispersed, and the amount thereof is only required to be dispersible.
S2, coating;
uniformly coating the positive electrode slurry obtained in the step S1 on the surface of a positive electrode current collector, wherein the coating surface density of the slurry is 20.0mg/cm 2 ～40.0mg/cm 2 ；
S3, drying;
the drying process conditions are that the temperature is 80-100 ℃ and the drying time is 6-8 hours;
s4, extruding the dried positive plate until the compacted density is 2.4g/cm 3 ～2.7g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the According to the invention, the compaction density is improved through the cooperation of the composite material and extrusion, and the energy density of the lithium iron phosphate battery is improved.
Wherein the inorganic filler is nano particles, and the extruded Cheng Haiyuan graphene oxide/lithium iron phosphate composite material moves in the positive plate;
s5, punching and drying to obtain the positive plate.
The negative electrode plate is obtained by coating and drying a second slurry, and the second slurry is mainly prepared from the following raw materials in percentage by weight:
90-95% of artificial graphite, 1-3% of carboxymethyl cellulose, 1-3% of styrene butadiene rubber and 1-5% of ketjen black.
Further, in step S1, the positive electrode slurry is mainly prepared from the following raw materials in parts by weight:
90-95 parts of reduced graphene oxide/lithium iron phosphate composite material;
1-2 parts of conductive agent;
2-3 parts of adhesive;
0.1 to 0.5 part of dispersing agent;
0.5 to 0.8 part of inorganic filler;
wherein the inorganic filler is alumina nano particles. According to the invention, the aluminum oxide nano particles are used, and the high hardness performance of the aluminum oxide nano particles is utilized to be matched with the internal arrangement and compaction of the coating, in which the reduced graphene oxide of the sheet layer and the flaky lithium iron phosphate nano particles are adaptive in synchronization in the extrusion process of the positive plate, so that the tap density of the positive plate is effectively improved.
The preparation method of the preferable reduced graphene oxide/lithium iron phosphate composite material comprises the following steps:
s11, chelating lithium acetate, graphene oxide/EDTA to form Fe 3+ And ammonium dihydrogen phosphate are dispersed in deionized water according to stoichiometric ratio, uniformly mixed, the pH value of the solution is regulated to 6.8-7.2, and the solution is added into a reaction kettle for hydrothermal reaction to obtain a precursor;
preferably, the process conditions of the hydrothermal reaction in the step S11 are as follows:
preserving heat for 5-8 hours at 200-215 ℃.
S12, heat treating the obtained precursor;
the heat treatment process is that the temperature is raised to 700 ℃ to 800 ℃ at the room temperature at the temperature rising speed of 5 ℃/min to 8 ℃/min, and the heat is preserved for 5h to 8h and then is cooled to the room temperature along with the furnace; and obtaining the lithium iron phosphate nano particles loaded on the surface of the graphene in a flake manner, namely the reduced graphene oxide/lithium iron phosphate composite material.
In the prior art, the conductivity of the lithium iron phosphate is poor, and because of the special olivine structure, tetrahedrons formed by P and O separate octahedrons formed by Fe and O, and the electronic conductivity of the lithium iron phosphate is only 10 -10 S*m -1 The conductivity between the lithium iron phosphate particles is extremely poor, and lithium ions can only be transmitted in the lithium iron phosphate particles through the specific axial direction on the specific surface of the lithium iron phosphate crystal, so that the diffusion of lithium ions from the interior into the electrolyte is severely restricted, the rate of oxidation-reduction reaction is greatly reduced, and even if electrons are transmitted to the reaction sites of the active substances at an extremely rapid rate, the rate of oxidation-reduction reaction is greatly reducedThe whole reaction cannot be carried out due to the slow release rate of lithium ions; the technical problems limit the transmission of electrons and lithium ions, thereby limiting the application of lithium iron phosphate in an optical storage integrated system; aiming at the technical problems, the invention utilizes the property of relatively good dispersibility of graphene oxide in water, utilizes hydrogen bonds to branch disodium ethylenediamine tetraacetate on the circumference of the graphene oxide, and then utilizes disodium ethylenediamine tetraacetate to chelate ferric ions to realize the preset generation position of lithium iron phosphate particles; EDTA is used as a complexing agent in a liquid environment of the hydrothermal reaction, and EDTA-2Na effectively keeps the surrounding of particles on graphene oxide in the process of precursor formation, and lithium iron phosphate and graphene oxide are relatively uniformly dispersed; forming surrounding distribution of the lithium iron phosphate precursor on graphene oxide; along with high-temperature calcination, EDTA is used as a reducing agent to form carbon and nitrogen in the calcination process, and Fe is added into the catalyst 3+ Reduction to Fe 2+ And the lithium iron phosphate is formed by combining the reduced graphene oxide with lithium ions and phosphate ions, so that the load of the reduced graphene oxide on the lithium iron phosphate nanosheets is effectively formed.
According to the invention, the iron source is chelated and positioned by utilizing graphene oxide and disodium ethylenediamine tetraacetate, so that the uniform position relationship between the graphene oxide and the generated lithium iron phosphate is effectively ensured, the sheet lithium iron phosphate loaded by the reduced graphene oxide is prepared, and the compaction density of the obtained positive plate is promoted by matching with inorganic filler particles and extrusion.
The composite material obtained by the invention has uniform particle size distribution, good dispersibility and stable structure, the ionic conductivity of the nanoscale lithium iron phosphate is obviously improved, the lithium iron phosphate is loaded by the reduced graphene oxide, and the electronic conductivity of the lithium iron phosphate is also obviously improved; the reduced graphene oxide/lithium iron phosphate positive electrode material has stable structure in cyclic use, the shape and the size of lithium iron phosphate are uniform, the particle size is between 100 and 300nm, and the lithium iron phosphate nano particles with sheet structures effectively utilize the increase of specific surface area to reduce lithium ions in LiFePO (lithium ion phosphate) 4 The internal transmission path is one-dimensional, the conduction of electrons and ions is rapid, and the phenomenon that particles are gathered, the structure collapses or the lithium ions are not timely extracted is restrainedIs not limited, and the capacity loss of Li of (C) is not limited. According to the invention, the lithium iron phosphate with a flaky structure loaded on the reduced graphene oxide effectively eliminates gaps in the extrusion process by matching with the production step of extrusion and increasing the tap density, meanwhile, the compacted lithium iron phosphate is loaded and supported by graphene, and the lithium iron phosphate still keeps a space for soaking electrolyte as an electrode active substance, has small volume expansion, and simultaneously, the ionic conductivity and the electronic conductivity of the lithium iron phosphate are promoted.
Preferably graphene oxide/EDTA chelated Fe 3+ The preparation method of (2) comprises the following steps:
s21, adding graphene oxide (namely GO) into an ethylene diamine tetraacetic acid disodium (namely EDTA-2 Na) solution, performing ultrasonic dispersion, uniformly mixing, adding ethanol, and drying under an infrared lamp to obtain EDTA/graphene oxide connected through hydrogen bonds;
in the step S21, ethanol is added to play a role in dispersing, so that the mixture can be dispersed.
Wherein EDTA is connected to graphene oxide through hydrogen bonds in the following manner:
；
s22, dispersing the EDTA/graphene oxide obtained in the step S1 into deionized water, and dripping Fe (NO 3 ) 3 Stirring the solution uniformly, and standing to obtain the graphene oxide/EDTA chelated Fe 3+ Dispersion of Fe in 3+ As EDTA is distributed around EDTA.
Further, in step S22, fe (NO 3 ) 3 Solute Fe (NO) contained in the solution 3 ) 3 The molar ratio of disodium ethylenediamine tetraacetate (namely EDTA-2 Na) in the step S21 is 1: (8-10). The EDTA-2Na is fully used in the invention, and the EDTA-2Na can effectively play roles of a complexing agent and a reducing agent.
Preferably, in step S11, the molar ratio of lithium, iron and phosphate is (1.0-1.05): 1.0:1.0. On the basis of the stoichiometric ratio, lithium can be slightly excessive, which is beneficial to the reaction.
The steps ofThe mass of graphene oxide in step S21 accounts for lithium acetate (lithium source) in step S11, and Fe (NO) in step S22 3 ) 3 The percentage of the total mass of the ammonium dihydrogen phosphate (phosphate) in the (iron source) and the step S11 is 5.0-5.0 wt.0 wt%. The graphene oxide effectively ensures the loading of lithium iron phosphate and promotes the dispersion of flaky lithium iron phosphate.
Preferably, the graphene oxide in step S21 is subjected to a pretreatment of uniform dispersion, and the pretreatment includes the following steps:
a1, carrying out microwave treatment on graphene oxide, removing moisture and increasing interlayer spacing;
a2, dispersing the graphene oxide treated by the A1 in an oxidizing electrolyte, respectively applying a constant voltage of 12-15V between a cathode and an anode, and decomposing water molecules to generate hydroxyl free radicals, wherein the surface oxidation groups of the graphene oxide sheet layer are increased;
and A3, stopping applying voltage, filtering, cleaning, collecting and drying to obtain the pretreated graphene oxide.
According to the preparation method, through pretreatment, the oxidized groups of the graphene oxide are further stripped and increased, so that the surrounding of the ethylene diamine tetraacetic acid on the flaky graphene oxide is promoted, and meanwhile, the graphene oxide is better in dispersibility in water and more sufficient in load.
Preferably, in the step A1, the microwave power is 500-800W, and the microwave time is 3-6 min.
In step A2, the electrolyte in the oxidizing electrolyte is hydrogen peroxide, sulfuric acid or concentrated sulfuric acid, and the concentration of the electrolyte is 0.5mol/L to 0.8mol/L. The invention utilizes the oxidizing electrolyte to promote the increase of the number of oxygen-containing groups on the surface of the graphene oxide.
The lithium ion battery prepared by the preparation method has high tap density and improves both electronic conductivity and ion conductivity.
By adopting the technical scheme, the invention has the beneficial effects that:
according to the invention, the sheet lithium iron phosphate nano particles loaded by the reduced graphene oxide are matched with extrusion rearrangement in the preparation process of the pole piece, so that the expansion of the pole piece after the electrolyte is infiltrated can be avoided while the tap density is improved; the main inventive concept is as follows: the flaky lithium iron phosphate is uniformly distributed on the reduced graphene oxide with the lamellar structure, and in the extrusion compaction process, the lithium iron phosphate in the micro-area is limited by the reduced graphene oxide to be effectively compacted, so that excessive extrusion of lithium iron phosphate serving as an active substance is avoided, the tap density is improved, meanwhile, an electrolyte infiltration channel is reserved, the transfer of electrons and ions is ensured, and the internal structure is stable; therefore, the lithium ion battery obtained by the invention has stable circulation and small direct current impedance change in the circulation process.
Drawings
FIG. 1 is an SEM image of a reduced graphene oxide/lithium iron phosphate composite material prepared according to example 1 of the present invention;
FIG. 2 is an XRD pattern of the reduced graphene oxide/lithium iron phosphate composite material prepared in example 1 of the invention;
FIG. 3 is an infrared spectrum of EDTA-2Na attached to the surface of graphene oxide in example 1 of this invention;
fig. 4 is a cycle and rate performance curve of lithium ion batteries according to the present invention, which are obtained in example 7, example 8, and comparative example.
Detailed Description
In order to further explain the technical scheme of the invention, the invention is explained in detail by specific examples.
According to the invention, by utilizing the relatively good dispersibility of graphene oxide in water, disodium ethylenediamine tetraacetate is grafted on the circumference of the graphene oxide by utilizing a hydrogen bond, and then the ferric iron ions are chelated by utilizing disodium ethylenediamine tetraacetate, so that the generation position of lithium iron phosphate particles is preset; EDTA is used as a complexing agent in a liquid environment of the hydrothermal reaction, and EDTA-2Na effectively keeps the surrounding of particles on graphene oxide in the process of precursor formation, and lithium iron phosphate and graphene oxide are relatively uniformly dispersed;
forming surrounding distribution of the lithium iron phosphate precursor on graphene oxide; along with high-temperature calcination, EDTA is used as a reducing agent to form carbon and nitrogen in the calcination process, and Fe is added into the catalyst 3+ Reduction to Fe 2+ And the lithium iron phosphate is formed by combining the reduced graphene oxide with lithium ions and phosphate ions, so that the load of the reduced graphene oxide on the lithium iron phosphate nanosheets is effectively formed. The composite material obtained by the invention has uniform particle size distribution, good dispersibility, stable structure and remarkably improved ionic conductivity of nano-scale lithium iron phosphate under partial state of charge (PSoC), and the electronic conductivity of the nano-scale lithium iron phosphate is remarkably improved when the nano-scale lithium iron phosphate is loaded by the reduced graphene oxide; the reduced graphene oxide/lithium iron phosphate anode has stable structure in cyclic use, the shape and the size of the lithium iron phosphate are uniform, the particle size is between 100 and 300nm, and the lithium iron phosphate nano particles with sheet structures effectively utilize the increase of specific surface area to reduce the lithium ions in LiFePO (lithium ion phosphate) 4 The internal transmission path is one-dimensional restriction, the conduction of electrons and ions is rapid, and the capacity loss of Li caused by particle aggregation, structural collapse or untimely lithium ion deintercalation is restrained. According to the invention, the sheet lithium iron phosphate nano particles loaded by the reduced graphene oxide are matched with the sheet lithium iron phosphate nano particles to be extruded and rearranged in the preparation process of the electrode sheet, so that the electrode sheet expansion after the electrolyte is infiltrated can be avoided while the tap density is improved; the main inventive concept is as follows: the flaky lithium iron phosphate is uniformly distributed on the reduced graphene oxide with the lamellar structure, and in the extrusion compaction process, the lithium iron phosphate in the micro-area is limited by the reduced graphene oxide to be effectively compacted, so that excessive extrusion of lithium iron phosphate serving as an active substance is avoided, the tap density is improved, meanwhile, an electrolyte infiltration channel is reserved, the transfer of electrons and ions is ensured, and the internal structure is stable; therefore, the lithium ion battery obtained by the invention has stable circulation and small direct current impedance change.
Example 1
The embodiment discloses a preparation method of a reduced graphene oxide/lithium iron phosphate composite material, which comprises the following steps:
s11, chelating lithium acetate, graphene oxide/EDTA to form Fe 3+ And ammonium dihydrogen phosphate are dispersed in deionized water according to stoichiometric ratio, uniformly mixed, the pH value of the solution is regulated to 6.8, and the solution is added into a reaction kettle for hydrothermal reaction to obtain a precursor;
the process conditions of the hydrothermal reaction in S11 in this embodiment are as follows:
the temperature is kept at 200 ℃ for 8 hours.
S12, performing heat treatment on the obtained precursor;
the heat treatment process is that the temperature is raised to 700 ℃ at the room temperature at the temperature rising speed of 5 ℃/min to 8 ℃/min, and the temperature is kept for 8 hours and then is cooled to the room temperature along with the furnace; and obtaining the lithium iron phosphate nano particles loaded on the surface of the graphene in a flake manner.
The scanning electron microscope of the reduced graphene oxide/lithium iron phosphate composite material prepared in this example is shown in fig. 1, and the XRD test is shown in fig. 2.
Graphene oxide/EDTA chelated Fe in this example 3+ The preparation method of the (C) comprises the following steps:
s21, adding graphene oxide into an ethylene diamine tetraacetic acid disodium solution, performing ultrasonic dispersion, uniformly mixing, adding ethanol, and drying under an infrared lamp to obtain EDTA/graphene oxide connected through hydrogen bonds;
wherein EDTA is connected to graphene oxide through hydrogen bonds in the following manner:
；
s22, dispersing the EDTA/graphene oxide obtained in the step S1 into deionized water, and dripping Fe (NO 3 ) 3 Stirring the solution uniformly, and standing to obtain the graphene oxide/EDTA chelated Fe 3+ Dispersion of Fe in 3+ As EDTA is distributed around EDTA.
The invention realizes the relative positioning between graphene oxide and ferric ion by utilizing hydrogen bond and chelation, and is beneficial to the formation of target products. FIG. 3 is an IR spectrum of EDTA-2Na/GO, from which GO can be seen at 3388 cm -1 A stretching vibration broad peak of-OH is formed at the position; at 1719 cm -1 A bending vibration peak with c=o; at 1631 and 1631 cm -1 A stretching vibration peak with C=C is arranged at the position; at 1402 cm -1 A C-OH stretching vibration peak is arranged at the position; at 1056 and 1056 cm -1 There is a C-O-C stretching vibration peak. At 3 459The N-H stretching vibration peak, the stretching vibration peak of C=O in-NHCO-functional group of 1 636 and the stretching vibration peak of C-O of 1 086cm < -1 > show that EDTA is effectively connected to the surface of GO.
In step S22 of the present embodiment, fe (NO 3 ) 3 Solute Fe (NO) contained in the solution 3 ) 3 The molar ratio of disodium ethylenediamine tetraacetate (namely EDTA-2 Na) in the step S21 is 1:8. the EDTA-2Na is fully used in the invention, and the EDTA-2Na can effectively play roles of a complexing agent and a reducing agent.
In step S11 described in this example, the molar ratio of lithium, iron and phosphate was 1.05:1.0:1.0.
The graphene oxide in the step S21 accounts for lithium acetate (lithium source) in the step S11 and Fe (NO) in the step S22 3 ) 3 The percentage of the total mass of ammonium dihydrogen phosphate (phosphate) in (iron source) and step S11 was 5.0. 5.0 wt%. The graphene oxide effectively ensures the loading of lithium iron phosphate and promotes the dispersion of flaky lithium iron phosphate.
Example 2
The embodiment discloses a preparation method of a reduced graphene oxide/lithium iron phosphate composite material, which comprises the following steps:
s11, chelating lithium acetate, graphene oxide/EDTA to form Fe 3+ And ammonium dihydrogen phosphate are dispersed in deionized water according to stoichiometric ratio, uniformly mixed, the pH value of the solution is regulated to 7.2, and the solution is added into a reaction kettle for hydrothermal reaction to obtain a precursor;
the process conditions of the hydrothermal reaction in S11 in this embodiment are as follows:
the temperature is kept at 215 ℃ for 5 hours.
Performing heat treatment on the obtained precursor;
the heat treatment process is that the temperature is raised to 800 ℃ at room temperature at a temperature raising speed of 5-8 ℃/min, and the heat is preserved for 5h and then is cooled to the room temperature along with the furnace; and obtaining the lithium iron phosphate nano particles loaded on the surface of the graphene in a flake manner.
Graphene oxide/EDTA chelated Fe in this example 3+ The preparation method of the (C) comprises the following steps:
s21, adding graphene oxide into an ethylene diamine tetraacetic acid disodium solution, performing ultrasonic dispersion, uniformly mixing, adding ethanol, and drying under an infrared lamp to obtain EDTA/graphene oxide connected through hydrogen bonds;
wherein EDTA is connected to graphene oxide through hydrogen bond in the following way
；
S22, dispersing EDTA/graphene oxide in deionized water, and dripping Fe (NO) 3 ) 3 Stirring the solution uniformly, and standing to obtain the graphene oxide/EDTA chelated Fe 3+ Dispersion of Fe in 3+ As EDTA is distributed around EDTA. The invention realizes the relative positioning between graphene oxide and ferric ion by utilizing hydrogen bond and chelation, and is beneficial to the formation of target products.
In this example Fe (NO) 3 ) 3 The molar ratio of EDTA-2Na is 1:10. the EDTA-2Na is fully used in the invention, and the EDTA-2Na can effectively play roles of a complexing agent and a reducing agent.
The molar ratio of lithium, iron and phosphate in S11 described in this example was 1.05:1.0:1.0.
The graphene oxide accounts for 8.0wt% of the total mass of the lithium source, the iron source and the phosphate. The graphene oxide effectively ensures the loading of lithium iron phosphate and promotes the dispersion of flaky lithium iron phosphate.
Example 3
The main difference between this example and the reduced graphene oxide/lithium iron phosphate composite material of example 1 is that the graphene oxide in S21 is subjected to a pretreatment of uniform dispersion, and the pretreatment includes the following steps:
a1, carrying out microwave treatment on graphene oxide, removing moisture and increasing interlayer spacing;
a2, dispersing the graphene oxide treated by the method A1 in an oxidizing electrolyte, respectively applying 12V constant voltage between a cathode and an anode, and decomposing water molecules to generate hydroxyl free radicals, wherein the surface oxidation groups of graphene oxide sheets are increased;
and A3, stopping applying voltage, filtering, cleaning, collecting and drying to obtain the pretreated graphene oxide. The method further peels off and increases the oxidation group of the graphene oxide, promotes the surrounding of the disodium ethylenediamine tetraacetate on the flaky graphene oxide, and simultaneously has better dispersibility of the graphene oxide in water and more sufficient load.
In step A2 of this example, the electrolyte in the oxidizing electrolyte solution was hydrogen peroxide, and the concentration of the electrolyte was 0.8mol/L. The invention utilizes the oxidizing electrolyte to promote the increase of the number of oxygen-containing groups on the surface of the graphene oxide.
In the embodiment, the microwave power in the step A1 is 500W, and the microwave time is 6min.
Example 4
The main difference between this embodiment and the reduced graphene oxide/lithium iron phosphate composite material of embodiment 2 is that graphene oxide is subjected to a pretreatment of uniform dispersion in step one, and the pretreatment includes the following steps:
a1, carrying out microwave treatment on graphene oxide, removing moisture and increasing interlayer spacing;
a2, dispersing the graphene oxide treated by the method A1 in an oxidizing electrolyte, respectively applying a constant voltage of 15V between a cathode and an anode, and decomposing water molecules to generate hydroxyl free radicals, wherein the surface oxidation groups of the graphene oxide sheet layers are increased;
and A3, stopping applying voltage, filtering, cleaning, collecting and drying to obtain the pretreated graphene oxide. The method further peels off and increases the oxidation group of the graphene oxide, promotes the surrounding of the disodium ethylenediamine tetraacetate on the flaky graphene oxide, and simultaneously has better dispersibility of the graphene oxide in water and more sufficient load.
In the step A2 of this example, the electrolyte in the oxidizing electrolyte was sulfuric acid, and the concentration of the electrolyte was 0.5mol/L. The invention utilizes the oxidizing electrolyte to promote the increase of the number of oxygen-containing groups on the surface of the graphene oxide.
In the embodiment, the microwave power in the step A1 is 800W, and the microwave time is 3min.
Example 5
The reduced graphene oxide/lithium iron phosphate composite material prepared in example 1 is assembled into a battery, wherein the lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the preparation method of the positive plate comprises the following steps:
s1, pulping;
mixing the reduced graphene oxide/lithium iron phosphate composite particles, a conductive agent, a binder, a dispersing agent and an inorganic filler, uniformly stirring, and dispersing the mixture by using deionized water to obtain positive electrode slurry; wherein the reduced graphene oxide/lithium iron phosphate composite material is a flaky lithium iron phosphate nanoparticle in-situ grown on the surface of the reduced graphene oxide;
the positive electrode slurry is mainly prepared from the following raw materials in parts by weight:
95 parts of reduced graphene oxide/lithium iron phosphate composite material;
2 parts of conductive carbon black serving as a conductive agent;
2 parts of binder SBR;
0.5 parts of dispersant CMC;
0.5 parts of alumina nano particles;
s2, coating;
uniformly coating the positive electrode slurry on the surface of a positive electrode current collector, wherein the coating surface density of the slurry is 35mg/cm 2 ；
S3, drying;
the drying process conditions are that the temperature is 100 ℃ and the drying time is 8 hours;
s4, extruding the dried positive plate until the compacted density is 2.68g/cm 3 ；
Wherein the inorganic filler is nano particles, and the extruded Cheng Haiyuan graphene oxide/lithium iron phosphate composite material moves in the positive plate;
s5, punching and drying to obtain the positive plate.
The negative electrode plate is obtained by coating and drying a second slurry, and the second slurry is mainly prepared from the following raw materials in percentage by weight: 92% of artificial graphite, 3% of carboxymethyl cellulose, 1% of styrene butadiene rubber and 4% of ketjen black.
And (3) laminating the obtained positive plate and negative plate, assembling, injecting liquid, forming, standing, separating the volume, and aging to obtain the lithium ion battery.
Example 6
The reduced graphene oxide/lithium iron phosphate composite material prepared in example 2 is assembled into a battery, wherein the lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the preparation method of the positive plate comprises the following steps:
s1, pulping;
mixing the reduced graphene oxide/lithium iron phosphate composite particles, a conductive agent, a binder, a dispersing agent and an inorganic filler, uniformly stirring, and dispersing the mixture by using deionized water to obtain positive electrode slurry; wherein the reduced graphene oxide/lithium iron phosphate composite material is a flaky lithium iron phosphate nanoparticle in-situ grown on the surface of the reduced graphene oxide;
the slurry for preparing the positive plate comprises the following substances in parts by mass:
94 parts of reduced graphene oxide/lithium iron phosphate composite material;
2 parts of conductive carbon black serving as a conductive agent;
3 parts of binder SBR;
0.2 parts of dispersant CMC;
0.8 parts of alumina nano particles;
s2, coating;
uniformly coating the positive electrode slurry on the surface of a positive electrode current collector, wherein the coating surface density of the slurry is 38mg/cm 2 ；
S3, drying;
the drying process conditions are that the temperature is 100 ℃ and the drying time is 8 hours;
s4, extruding the dried positive plate until the compacted density is 2.66g/cm 3 ；
Wherein the inorganic filler is nano particles, and the extruded Cheng Haiyuan graphene oxide/lithium iron phosphate composite material moves in the positive plate;
s5, punching and drying to obtain the positive plate.
The negative electrode plate is obtained by coating and drying a second slurry, and the second slurry is mainly prepared from the following raw materials in percentage by weight:
92% of artificial graphite, 3% of carboxymethyl cellulose, 1% of styrene butadiene rubber and 4% of ketjen black.
And (3) laminating the obtained positive plate and negative plate, assembling, injecting liquid, forming, standing, separating the volume, and aging to obtain the lithium ion battery.
Example 7
Assembling the reduced graphene oxide/lithium iron phosphate composite material prepared in the embodiment 3 into a battery, wherein the lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the preparation method of the positive plate comprises the following steps:
s1, pulping;
mixing the reduced graphene oxide/lithium iron phosphate composite particles, a conductive agent, a binder, a dispersing agent and an inorganic filler, uniformly stirring, and dispersing the mixture by using deionized water to obtain positive electrode slurry; wherein the reduced graphene oxide/lithium iron phosphate composite material is a flaky lithium iron phosphate nanoparticle in-situ grown on the surface of the reduced graphene oxide;
the slurry for preparing the positive plate comprises the following substances in parts by mass:
95 parts of reduced graphene oxide/lithium iron phosphate composite material;
2 parts of conductive carbon black serving as a conductive agent;
2.5 parts of binder SBR;
0.5 parts of dispersant CMC;
0.2 parts of inorganic filler alumina nano particles;
s2, coating;
uniformly coating the positive electrode slurry on the surface of a positive electrode current collector, wherein the coating surface density of the slurry is 37mg/cm 2 ；
S3, drying;
the drying process conditions are that the temperature is 100 ℃ and the drying time is 8 hours;
s4, extruding the dried positive plate until the compaction density is 2.57g/cm 3 ；
Wherein the inorganic filler is nano particles, and the extruded Cheng Haiyuan graphene oxide/lithium iron phosphate composite material moves in the positive plate;
s5, punching and drying to obtain the positive plate.
The slurry for coating and drying the negative plate comprises the following components in percentage by mass:
92% of artificial graphite, 3% of carboxymethyl cellulose, 1% of styrene butadiene rubber and 4% of ketjen black.
And (3) laminating the obtained positive plate and negative plate, assembling, injecting liquid, forming, standing, separating the volume, and aging to obtain the lithium ion battery.
Example 8
Assembling the reduced graphene oxide/lithium iron phosphate composite material prepared in the embodiment 4 into a battery, wherein the lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the preparation method of the positive plate comprises the following steps:
s1, pulping;
mixing the reduced graphene oxide/lithium iron phosphate composite particles, a conductive agent, a binder, a dispersing agent and an inorganic filler, uniformly stirring, and dispersing the mixture by using deionized water to obtain positive electrode slurry; wherein the reduced graphene oxide/lithium iron phosphate composite material is a flaky lithium iron phosphate nanoparticle in-situ grown on the surface of the reduced graphene oxide;
the slurry for preparing the positive plate comprises the following substances in parts by mass:
94 parts of reduced graphene oxide/lithium iron phosphate composite material;
2 parts of conductive carbon black serving as a conductive agent;
3 parts of binder SBR;
0.4 parts of dispersant CMC;
0.6 parts of alumina nano particles;
s2, coating;
uniformly coating the positive electrode slurry on the surface of a positive electrode current collector, wherein the coating surface density of the slurry is 39mg/cm 2 ；
S3, drying;
the drying process conditions are that the temperature is 100 ℃ and the drying time is 8 hours;
s4, extruding the dried positive plate until the compacted density is 2.70g/cm 3 ；
Wherein the inorganic filler is nano particles, and the extruded Cheng Haiyuan graphene oxide/lithium iron phosphate composite material moves in the positive plate;
s5, punching and drying to obtain the positive plate.
The slurry for coating and drying the negative plate comprises the following components in percentage by mass:
92% of artificial graphite, 3% of carboxymethyl cellulose, 1% of styrene butadiene rubber and 4% of ketjen black.
And (3) laminating the obtained positive plate and negative plate, assembling, injecting liquid, forming, standing, separating the volume, and aging to obtain the lithium ion battery.
Comparative example
The comparative example comprises the following steps:
s11, dispersing equal amounts of graphene oxide, lithium acetate, ferric nitrate and ammonium dihydrogen phosphate in deionized water according to stoichiometric ratio, uniformly mixing, and adding into a reaction kettle for hydrothermal reaction to obtain a precursor;
the process conditions of the hydrothermal reaction in S11I in this comparative example are:
the temperature is kept at 200 ℃ for 8 hours.
S12, performing heat treatment on the obtained precursor;
the heat treatment process is that the temperature is raised to 700 ℃ at the room temperature at the temperature rising speed of 5 ℃/min to 8 ℃/min, and the temperature is kept for 8 hours and then is cooled to the room temperature along with the furnace; and obtaining the reduced graphene oxide/lithium iron phosphate composite material.
The graphene/lithium iron phosphate composite material prepared in the comparative example is assembled into a battery, and the lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the preparation method of the positive plate comprises the following steps:
s1, pulping;
mixing the reduced graphene oxide/lithium iron phosphate composite particles, conductive carbon black serving as a conductive agent, SBR serving as a binder and CMC serving as a dispersing agent, uniformly stirring, and dissolving the mixture in deionized water for dispersion to obtain anode slurry; the slurry for preparing the positive plate comprises the following substances in parts by mass:
95 parts of reduced graphene oxide/lithium iron phosphate composite material;
2.5 parts of a conductive agent;
2 parts of a binder;
0.5 parts of dispersing agent;
s2, coating;
uniformly coating the positive electrode slurry on the surface of a positive electrode current collector, wherein the coating surface density of the slurry is 38mg/cm 2 ；
S3, drying;
the drying process conditions are that the temperature is 100 ℃ and the drying time is 8 hours;
s4, punching and drying to obtain a positive plate, wherein the compaction density of the obtained positive plate is 2.02 g/cm 3 . The reduced graphene oxide/lithium iron phosphate composite material used in the comparative example herein was poor in dispersibility, and the resulting pole piece was low in compacted density without the operation of co-compaction.
The slurry for coating and drying the negative plate comprises the following components in percentage by mass:
92% of artificial graphite, 3% of carboxymethyl cellulose, 1% of styrene butadiene rubber and 4% of ketjen black.
And (3) laminating the obtained positive plate and negative plate, assembling, injecting liquid, forming, standing, separating the volume, and aging to obtain the lithium ion battery.
Specific surface areas of the graphene/lithium iron phosphate composites obtained in test examples 1 to 4 and comparative example are shown in table 1.
Table 1 specific surface area of graphene/lithium iron phosphate composite materials obtained in examples 1 to 4 and comparative example
The electrochemical properties of the lithium ion batteries produced in examples 5 to 8 and comparative example were respectively tested, and the dc resistance increase ratio, r= (DCR), was shown in table 2 500 -DCR 1 ）/DCR 1 *100%; the specific test method comprises the following steps:
charging the battery at 25deg.C constant current to 3.65V, charging at constant voltage of 3.65V to current of 0.05C, standing for 5min, and recording voltage V 1 . Then discharge for 30s with 1/3C, record voltage V 2 Then (V) 2 -V 1 ) 1/3C, and obtaining the direct current impedance of the battery after the first and 500 th cycles.
Table 2 dc impedance variation of the batteries obtained in examples 5 to 8 and comparative example
The extrusion and non-extrusion in table 2 show the dc impedance variation of the battery produced by the preparation method with the extrusion step of S4 and the extrusion step without S4, respectively, indicating that the extrusion step has a significant effect on reducing the dc impedance of the battery. Examples 5-8 were all extrusion-processed, and the non-extruded data in Table 2 were based on examples 5-8, omitting the DC impedance data of the cells obtained in the extrusion step.
The batteries obtained in examples 7, 8 and comparative examples were tested for 0.2C, 0.5C, 1C, 2C and 5C cycle and rate performance curves, respectively, as shown in fig. 4.
As can be seen from the differences of the manufacturing process parameters of fig. 1 to 4, tables 1 and 2 and the respective examples and comparative examples, the comparative examples directly use graphene oxide to mix with a lithium source, an iron source and a phosphorus source to prepare a precursor hydrothermally, wherein the relative positions of the lithium iron phosphate precursor and the graphene oxide are not pre-positioned, and the relative dispersion of the lithium iron phosphate and the graphene oxide is not uniform and the dispersion of the graphene oxide to the lithium iron phosphate is insufficient in combination with the data of the specific surface area. Correspondingly, in the embodiment 7 and the embodiment 8, the dispersion of the lithium iron phosphate and the reduced graphene oxide in the corresponding battery positive plate is more uniform, the microstructure of the positive plate is stable, and the cycle performance and the multiplying power performance of the obtained lithium ion battery are more stable. The hydrogen bond connection between EDTA-2Na and graphene oxide was further increased by increasing the oxidation degree of graphene in examples 3 and 4, and further peeling and breaking occurred during the graphene oxide increased the oxidation group, so that the relative position between graphene and lithium iron phosphate precursor in examples 3 and 4 was dispersed more uniformly, and the reaction in the aqueous phase was also more sufficient, compared to examples 1 and 2.
As can be seen from FIGS. 1 and 2, liFePO obtained according to the present invention 4 The lithium ion battery positive electrode sheet obtained in the examples 5 to 8 has the advantages of uniform crystal particles, stable particle dispersion, stable structure, high compaction density, stable microstructure of the positive electrode sheet, and reduced alumina nano particles and reduced graphene oxide/lithium iron phosphate composite material matched with the positive electrode sheet, and the advantages of effectively arranging the microstructure in the compaction process, improving the compaction density, ensuring the ionic conductivity and the electronic conductivity, and small direct current impedance increase rate, and the lithium ion battery prepared in the example 7 has small direct current impedance change compared with the lithium ion batteries corresponding to the examples 5, 6 and 8, mainly because the consumption of the alumina nano particles is small, the composite material moves in the coating layer in the extrusion process, so that the promotion effect on the compaction of the electrode sheet is reduced, and is consistent with the cycle and multiplying power performance reflected by fig. 4.
The microstructure of the reduced graphene oxide/lithium iron phosphate anode is more stable after extrusion, the structure is stable in recycling, the shape and the size of the lithium iron phosphate are uniform, the particle size is between 100 and 300nm, and the lithium iron phosphate nano particles with the lamellar structure effectively utilize the increase of the specific surface area to reduce the lithium ions in LiFePO 4 The internal transmission path is one-dimensional, the conduction of electrons and ions is rapid, and the phenomenon that particles are gathered, the structure collapses or the lithium ions are not timely extracted is inhibitedThe resulting capacity loss of Li.
Claims (8)
1. A preparation method of a high-performance lithium ion battery for energy storage is characterized by comprising the following steps: the lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte;
the preparation method of the positive plate comprises the following steps:
s1, pulping;
mixing the reduced graphene oxide/lithium iron phosphate composite particles, a conductive agent, a binder, a dispersing agent and an inorganic filler, uniformly stirring, and dissolving the mixture in a solvent for dispersion to obtain anode slurry; wherein the reduced graphene oxide/lithium iron phosphate composite material is a flaky lithium iron phosphate nanoparticle in-situ grown on the surface of the reduced graphene oxide;
s2, coating;
uniformly coating the positive electrode slurry obtained in the step S1 on the surface of a positive electrode current collector, wherein the coating surface density of the slurry is 20.0mg/cm 2 ～40.0mg/cm 2 ；
S3, drying;
the drying process conditions are that the temperature is 80-100 ℃ and the drying time is 6-8 hours;
s4, extruding the dried positive plate until the compacted density is 2.4g/cm 3 ～2.7g/cm 3 ；
Wherein the inorganic filler is nano particles, and the extruded Cheng Haiyuan graphene oxide/lithium iron phosphate composite material moves in the positive plate;
s5, punching and drying to obtain a positive plate;
the preparation method of the reduced graphene oxide/lithium iron phosphate composite material comprises the following steps:
s11, chelating lithium acetate, graphene oxide/EDTA to form Fe 3+ And ammonium dihydrogen phosphate are dispersed in deionized water according to stoichiometric ratio, uniformly mixed, the pH value of the solution is regulated to 6.8-7.2, and the solution is added into a reaction kettle for hydrothermal reaction to obtain a precursor;
s12, heat treating the obtained precursor;
the heat treatment process is that the temperature is raised to 700 ℃ to 800 ℃ at the room temperature at the temperature rising speed of 5 ℃/min to 8 ℃/min, and the heat is preserved for 5h to 8h and then is cooled to the room temperature along with the furnace;
obtaining lithium iron phosphate nano particles loaded on the surface of graphene in a flake manner, namely a reduced graphene oxide/lithium iron phosphate composite material;
graphene oxide/EDTA chelated Fe 3+ The preparation method of the (C) comprises the following steps:
s21, adding graphene oxide into an ethylene diamine tetraacetic acid disodium solution, performing ultrasonic dispersion, uniformly mixing, adding ethanol, and drying under an infrared lamp to obtain EDTA/graphene oxide connected through hydrogen bonds;
wherein EDTA is connected to graphene oxide through hydrogen bonds in the following manner:
s22, dispersing the EDTA/graphene oxide obtained in the step S1 into deionized water, and dripping Fe (NO 3 ) 3 Stirring the solution uniformly, and standing to obtain graphene oxide/EDTA chelated Fe 3+ Dispersion of Fe in 3+ As EDTA is distributed around EDTA.
2. The method for preparing the high-performance lithium ion battery for energy storage according to claim 1, wherein the method comprises the following steps: in the step S1, the positive electrode slurry is prepared from the following raw materials in parts by weight:
wherein the inorganic filler is alumina nano particles.
3. Preparation of high-performance lithium ion battery for energy storage according to claim 1 or 2The method is characterized in that: in step S22, fe (NO 3 ) 3 Solute Fe (NO) contained in the solution 3 ) 3 The molar ratio of disodium ethylenediamine tetraacetate to the disodium in the step S21 is 1: (8-10).
4. The method for manufacturing a high-performance lithium ion battery for energy storage according to claim 1 or 2, characterized in that: in the step S11, the molar ratio of lithium to iron to phosphate radical is (1.0-1.05) 1.0:1.0;
the graphene oxide in the step S21 accounts for lithium acetate in the step S11 and Fe (NO) in the step S22 3 ) 3 And the percentage of the total mass of the ammonium dihydrogen phosphate in the step S11 is 5.0 to 8.0 percent by weight.
5. The method for manufacturing a high-performance lithium ion battery for energy storage according to claim 1 or 2, characterized in that: the process conditions of the hydrothermal reaction in S11 are as follows:
preserving heat for 5-8 hours at 200-215 ℃.
6. The method for manufacturing a high-performance lithium ion battery for energy storage according to claim 1 or 2, characterized in that: the graphene oxide in S21 is subjected to pretreatment of uniform dispersion, and the pretreatment comprises the following steps:
a1, carrying out microwave treatment on graphene oxide, removing moisture and increasing interlayer spacing;
a2, dispersing the graphene oxide treated by the A1 in an oxidizing electrolyte, respectively applying a constant voltage of 12-15V between a cathode and an anode, and decomposing water molecules to generate hydroxyl free radicals, wherein the surface oxidation groups of the graphene oxide sheet layer are increased;
and A3, stopping applying voltage, filtering, cleaning, collecting and drying to obtain the pretreated graphene oxide.
7. The method for preparing the high-performance lithium ion battery for energy storage according to claim 6, wherein the method comprises the following steps:
in the step A1, the microwave power is 500W-800W, and the microwave time is 3 min-6 min; and/or
In the step A2, the electrolyte in the oxidizing electrolyte is hydrogen peroxide or sulfuric acid, and the concentration of the electrolyte is 0.5mol/L to 0.8mol/L.
8. A lithium ion battery produced according to the production method of any one of claims 1 to 7.
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