CN107170977B - Preparation method of lithium iron phosphate/graphene composite material, lithium ion battery anode and lithium ion battery - Google Patents
Preparation method of lithium iron phosphate/graphene composite material, lithium ion battery anode and lithium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000008247 solid mixture Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- -1 iron ions Chemical class 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 19
- 239000010439 graphite Substances 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000001027 hydrothermal synthesis Methods 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 238000013329 compounding Methods 0.000 description 8
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- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 6
- 235000010703 Modiola caroliniana Nutrition 0.000 description 6
- 244000038561 Modiola caroliniana Species 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
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- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
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- 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
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- 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
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- 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
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/625—Carbon or graphite
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of a lithium iron phosphate/graphene composite material, a lithium ion battery anode and a lithium ion battery. The lithium iron phosphate/graphene composite material prepared by the invention is applied to a lithium ion battery, and has excellent performances of high capacity, long cycle life, low cost, easiness in large-scale production and the like.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a lithium iron phosphate/graphene composite material, a lithium ion battery anode and a lithium ion battery.
Background
New energy sources, such as wind energy, solar energy, geothermal energy, etc., have gained wide attention due to their advantages of being clean, efficient, renewable, etc. However, such dispersed, non-continuous energy is difficult to directly utilize and typically requires an energy storage system for storage. Chemical power sources are one of the most common energy storage systems in today's society. Among them, Lithium Ion Batteries (LIBs) have become a main development trend of chemical power sources due to their advantages of high specific energy, long cycle life, no memory effect, environmental friendliness, etc., and have been widely used in various fields such as portable electronic devices, electric vehicles, and aerospace. The positive electrode material is used as a core component of the power lithium ion battery, and the cost and the performance of the positive electrode material directly influence the overall cost and the performance of the battery. The transition metal phosphate has an open space for storing lithium, and is a novel lithium battery positive electrode material. For example LiFePO4The catalyst has the advantages of high specific capacity of 170mAh/g, low cost and low toxicity. But its conductivity is low (10)-9S/cm2) Poor lithium ion diffusion (10)-14～10-16cm2/s) leading to a rapid capacity fade upon high rate charge and discharge. The research shows that: the special two-dimensional high-specific-surface-area graphene structure and the excellent electron transmission capability thereof can effectively improve the conductivity of the positive electrode materialAnd the diffusion and transmission capacity of lithium ions is improved. Therefore, the development of a high-stability composite material cathode material with excellent performance and low price is the focus of lithium ion battery research.
Graphene is considered to be an ideal component of a composite electrode material as an advanced carbon material due to its superior electron conductivity, large specific surface area, and special two-dimensional structure. The three-dimensional graphene is formed by stacking single atomic layers of carbon, and has the advantages of ultralow density, high surface area, high heat conductivity, high temperature resistance, corrosion resistance, good ductility, good flexibility and the like. In recent years, with intensive research on graphene, it is found that good conductivity of graphene plays an important role in improving the performance of lithium ion batteries. The conductivity and the dispersibility of the composite material are improved by the three-dimensional graphene, and the electrolyte can be fully contacted with the active substance of the electrode material, so that the electrochemical performance of the three-dimensional graphene composite material is further improved.
LiFePO4Exists in nature in the form of ferrophosphorus lithium ore, belongs to an orthorhombic system, and has a space group of Pmnb. Each unit cell contains 4 lithium iron phosphate units, and the unit cell parameters are that a is 0.6008nm, b is 1.0324nm, and c is 0.4694 nm. Lithium iron phosphate has a stable, ordered olivine-type structure that: the oxygen atoms in the crystal structure are arranged in a slightly distorted hexagonal close packing mode, wherein Fe and Li are respectively positioned in the center of an oxygen atom octahedron to form FeO6Octahedron and LiO6Octahedron. P is in the center of the tetrahedron of oxygen atoms to form PO4The tetrahedron forms a stable-structure three-dimensional network structure connected through covalent bonds, so that the lithium iron phosphate as the anode material has good thermal stability and safety, and is particularly suitable for large-scale application. However, poor rate capability limits its practical application, which is determined by its own slow diffusion coefficient of lithium ions and low electronic conductivity. At present, methods such as surface conductive layer coating, ion doping, morphology optimization and the like are mostly adopted to solve the problem. Recent research work shows that the electronic conductivity of the material can be effectively improved and the rate capability of the material can be improved by compounding the lithium ion battery electrode material and the graphene. Therefore, the three-dimensional structure of the lithium iron phosphate/graphene is constructedThe composite material has the advantages that the flexible netted conductive structure of the graphene is utilized to improve the conductivity of the electrode material, and the rate capability of the material can be improved. Chinese invention patent (publication No. CN105514366A) "a nitrogen-doped graphene composite LiFePO4A preparation method of a lithium ion battery anode material' discloses a nitrogen-doped graphene composite LiFePO4The synthesis method of the material needs freeze drying and two-step high-temperature treatment, has high energy consumption and LiFePO4The distribution uniformity on graphene is poor, and large-scale synthesis is difficult. For example, LiFePO prepared in TianXiaohui et al (Journal of Power Sources,2017,340,40-50) by hydrothermal method and subsequent calcination4With graphene aerogel composites, LiFePO4The graphene aerogel is unevenly distributed on the surface and the bulk phase, so that the performance of the lithium ion battery is influenced. In summary, most of the existing graphene composite materials are in a mixed state of graphene and lithium iron phosphate, the lithium iron phosphate is unevenly distributed on the surface and inside of the graphene, and the lithium iron phosphate easily falls off from the graphene in the charging and discharging processes, so that the conductivity is reduced, and the performance of the lithium ion battery is finally affected.
Disclosure of Invention
In view of the defects in the prior art, the technical problem to be solved by the invention is to provide a preparation method of a lithium iron phosphate/graphene composite material, a lithium ion battery anode and a lithium ion battery. The three-dimensional reduced graphene oxide is prepared from low-price raw materials, and the lithium iron phosphate/graphene composite material is obtained through hydrothermal treatment, compounding and calcining. The invention provides a preparation method which is simple in process, high in yield and easy to expand production, aiming at improving the wide application of lithium iron phosphate as a lithium ion battery anode material and a graphene composite material.
A preparation method of a lithium iron phosphate/graphene composite material comprises the following steps:
A. dissolving an iron source, a phosphate source, a lithium source and a reducing agent in deionized water, uniformly stirring to obtain a soaking solution, and then dispersing the three-dimensional reduced graphene oxide in the soaking solution to prepare a mixed solution for standing;
the iron source in the step A is selected from one or more of ferrous chloride, ferrous sulfate, ferrous acetate and ferrous oxalate, the concentration of iron ions in the iron source in the mixed solution is 0.05-0.80 mol/L, the iron source is preferably ferrous chloride, and the concentration of the iron ions in the iron source in the mixed solution is preferably 0.15-0.40 mol/L;
in the step A, a phosphate radical source is selected from one or more of phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, the concentration of phosphate radicals in the mixed solution is 0.05-0.80 mol/L, phosphoric acid is preferably selected as the phosphate radical source, and the concentration of phosphate radicals in the mixed solution is preferably 0.15-0.40 mol/L;
in the step A, a lithium source is selected from one or more of lithium chloride, lithium sulfate, lithium nitrate and lithium acetate, the concentration of lithium ions in the lithium source in the mixed solution is 0.05-0.80 mol/L, the lithium source is preferably lithium chloride, and the concentration of lithium in the mixed solution is preferably 0.15-0.40 mol/L;
the mass ratio of iron ions, phosphate radicals and lithium ions in the soaking solution is 1:1: 1;
the reducing agent in the step A is selected from one or more of ascorbic acid, hydrazine hydrate and hydroxylamine hydrochloride, the concentration of the reducing agent in the soaking solution is 0.05-0.80 mol/L, the reducing agent is preferably ascorbic acid, and the concentration of the reducing agent in the mixed solution is preferably 0.15-0.40 mol/L;
in the step A, the concentration of the three-dimensional reduced graphene oxide in the mixed solution is 0.1-6.0 g/L, preferably 0.6-3.0 g/L;
the standing time in the step A is more than 1 day, preferably 1 to 3 days;
the temperature of the mixed solution is 3-80 ℃ when the mixed solution is placed in the step A, and preferably 10-30 ℃;
B. carrying out vacuum freeze drying on the placed mixed solution until the water is completely sublimated to prepare a solid mixture;
the freeze-drying temperature in the step B is-50 to 0 ℃, and the freeze-drying temperature is preferably-50 to-20 ℃; the freeze drying time is more than 2 days, and preferably 2-4 days; vacuum degree of vacuum freeze drying is less than 50 Pa;
C. pre-decomposing the solid mixture for 1-6 hours at 160-450 ℃ under the inert gas protective atmosphere to obtain a reaction precursor, and preferably pre-decomposing for 1-4 hours at 160-300 ℃; and roasting the reaction precursor for 24-36 hours at the temperature of 450-750 ℃ under the protection of inert gas to obtain a product, preferably roasting the reaction precursor for 24-30 hours at the temperature of 450-600 ℃ to obtain the lithium iron phosphate/graphene composite material.
The inert gas in the step C is selected from one or two of nitrogen and argon, preferably high-purity nitrogen;
the preparation method of the three-dimensional reduced graphene oxide in the step A comprises the following steps:
dispersing graphite oxide in water to prepare a graphite oxide suspension, adding concentrated sulfuric acid into the suspension, performing ultrasonic dispersion uniformly to prepare a mixed solution, then putting the mixed solution into a reaction kettle, reacting at 160-260 ℃ for 18-24 hours, preferably at 190-220 ℃ for 20-24 hours, and washing to obtain three-dimensional reduced graphene oxide;
the graphene oxide is synthesized by an improved Hummers method, and the specific steps are as follows:
5.0g of graphite and 3.75g of NaNO were weighed out separately3Placing into a 1L beaker, stirring with mechanical strength, slowly adding 150mL concentrated sulfuric acid, stirring for 0.5 hr, and slowly adding 20g KMnO4After the addition of the reaction mixture was completed in 0.5 hour, the stirring was stopped after further stirring for 20 hours because of the increase in the viscosity of the reaction mixture, to obtain a paste-like mauve substance. After standing for 5 days, 500mL of deionized water and 30mL of H were slowly added2O2When the solution color is changed into obvious bright yellow, centrifuging and washing after the solution fully reacts to obtain graphite oxide;
the concentration of the graphene oxide in the mixed solution is 0.75-1.5 g/L, preferably 1.0-1.25 g/L;
the concentration of the sulfuric acid in the mixed solution in the step is 1.2-2.5 mol/L, preferably 1.7-1.9 mol/L.
A lithium iron phosphate/graphene composite material is prepared by the preparation method of the lithium iron phosphate/graphene composite material;
a lithium ion battery anode is made of a lithium iron phosphate/graphene composite material.
A lithium ion battery is prepared from a lithium ion battery anode made of a lithium iron phosphate/graphene composite material.
The invention designs and synthesizes a novel lithium iron phosphate/graphene composite material aiming at the defects of slow lithium ion diffusion coefficient, low electronic conductivity and the like of lithium iron phosphate in the application of lithium ion batteries. On the one hand, three-dimensional graphene shortens lithium ions (Li)+) Diffusion distance in the crystal; on the other hand, the three-dimensional graphene effectively improves the electronic conductivity of the surface of the material, and is beneficial to the transmission of electrons in the composite material, so that the electrochemical performance of the composite material can be improved by compounding lithium iron phosphate and the graphene. According to the invention, the three-dimensional reduction graphene oxide is synthesized by a hydrothermal method, and is soaked in a soaking solution of an iron source, a phosphate source, a lithium source and a reducing agent, and the lithium iron phosphate and graphene composite material is obtained through low-temperature freeze drying and subsequent calcination.
The main innovation point of the method is that the three-dimensional reduced graphene oxide is used as a substrate, and lithium iron phosphate is uniformly loaded on the surface and in a pore channel structure of the three-dimensional reduced graphene oxide through low-temperature freeze drying and subsequent calcination.
Compared with the prior art, the invention has the following advantages:
(1) according to the prepared lithium iron phosphate and graphene composite material, the lithium iron phosphate is loaded on the surface of the three-dimensional graphene and in the pore structure, the three-dimensional porous structure promotes the composite material to be fully contacted with lithium ion electrolyte, the three-dimensional graphene plays a role in repairing and bridging a carbon layer, and the electrochemical performance of the lithium iron phosphate is further optimized;
(2) the prepared lithium iron phosphate and graphene composite material is stable in performance and high-temperature resistant, the conductivity of the material is improved by the graphene, and the three-dimensional porous structure constructs abundant gaps to provide a channel for the rapid transmission of lithium ions, so that the lithium ions can be transferred on the surface and reach reactive active sites, and the conductivity of the lithium iron phosphate is improved;
(3) the prepared lithium iron phosphate and graphene composite material has a large specific surface area, multiple folds on the surface of the three-dimensional graphene have a high specific surface area, a large number of load sites of the lithium iron phosphate are provided, the particle size of the lithium iron phosphate is reduced, and the diffusion rate of lithium ions is improved;
(4) the prepared lithium iron phosphate and graphene composite material is used for a lithium ion battery, and has the advantages of high capacity, good thermal stability, environmental protection, stable cycle and the like, high capacity and long cycle life;
(5) the method has the advantages of simple experimental steps, low requirements on instruments and equipment used for experiments, wide raw material sources, low cost and capability of batch production.
Drawings
Fig. 1 is an SEM image of the lithium iron phosphate/graphene composite material prepared in example 1;
fig. 2 is an SEM image of the lithium iron phosphate/graphene composite material prepared in example 2;
fig. 3 is an SEM image of the lithium iron phosphate/graphene composite material prepared in example 3;
fig. 4 is an XRD pattern of the lithium iron phosphate/graphene composite material prepared in example 3;
fig. 5 is an SEM image of the lithium iron phosphate/graphene composite material prepared in example 4;
fig. 6 is an SEM image of the lithium iron phosphate/graphene composite material prepared in example 5;
fig. 7 is a cycle stability test chart of the lithium iron phosphate/graphene composite material prepared in example 4 as a lithium ion battery positive electrode material at a current density of 0.1C.
Detailed Description
Example 1
The preparation method of the lithium iron phosphate and graphene composite material comprises the following steps:
a hydrothermal process: 5.0g of graphite and 3.75g of NaNO were weighed out separately3Placing into a 1L beaker, stirring with mechanical strength, slowly adding 150mL concentrated sulfuric acid, stirring for 0.5 hr, and slowly adding 20g KMnO4After the addition of the reaction mixture was completed in 0.5 hour, the stirring was stopped after further stirring for 20 hours because of the increase in the viscosity of the reaction mixture, to obtain a paste-like mauve substance. After standing for 5 days, 500mL of deionized water and 30mL of H were slowly added2O2When the solution color changes to more obvious bright yellowAnd after the solution fully reacts, centrifuging and washing to obtain the graphite oxide. 70mg of graphite oxide was dissolved in 80mL of deionized water, and 6mL of concentrated sulfuric acid (ρ ═ 1.84 g/cm) was added3) And ultrasonically dispersing for 3 hours, transferring the solution into a small glass bottle, averagely transferring the solution into 5 hydrothermal reaction kettles, reacting for 20 hours in a drying oven at 200 ℃, washing, and collecting to obtain 14mg of three-dimensional reduced graphene oxide.
A compounding procedure: 0.38g ferrous chloride and 0.12g lithium chloride were dissolved in 12mL deionized water, and 131.24 μ L concentrated phosphoric acid (ρ ═ 1.69 g/cm) was added3) And 109.78 μ L of hydrazine hydrate (ρ 1.03 g/cm)3) And after complete dissolution, putting 14mg of three-dimensional reduced graphene oxide into the solution, soaking in a water bath at 20 ℃ for 2 days, then transferring the solution and the three-dimensional reduced graphene oxide into a plastic beaker, freeze-drying at-50 ℃ for 4 days, pre-decomposing the obtained solid mixture for 3 hours at 160 ℃ in a high-purity nitrogen atmosphere to obtain a reaction precursor, and then roasting the reaction precursor for 30 hours at 500 ℃ in a high-purity nitrogen atmosphere to obtain the lithium iron phosphate/graphene composite material.
Example 2
The preparation method of the lithium iron phosphate and graphene composite material comprises the following steps:
a hydrothermal process: 5.0g of graphite and 3.75g of NaNO were weighed out separately3Placing into a 1L beaker, stirring with mechanical strength, slowly adding 150mL concentrated sulfuric acid, stirring for 0.5 hr, and slowly adding 20g KMnO4After the addition of the reaction mixture was completed in 0.5 hour, the stirring was stopped after further stirring for 20 hours because of the increase in the viscosity of the reaction mixture, to obtain a paste-like mauve substance. After standing for 5 days, 500mL of deionized water and 30mL of H were slowly added2O2And at the moment, the color of the solution is changed into obvious bright yellow, and after the solution is fully reacted, the solution is centrifuged and washed to obtain the graphite oxide. Dissolving 100mg of graphite oxide in 80mL of deionized water, adding 8mL of concentrated sulfuric acid, performing ultrasonic dispersion for 3 hours, transferring the solution into a small glass bottle, then averagely transferring the solution into 5 hydrothermal reaction kettles, reacting in an oven at 180 ℃ for 24 hours, washing, and collecting 20mg of three-dimensionally reduced graphene oxide.
A compounding procedure: will be 0.42Iron acetate (g), diammonium hydrogen phosphate (0.31 g) and lithium sulfate (0.15 g) were dissolved in 12mL of deionized water, and 137.22. mu.L of hydrazine hydrate (. rho. ═ 1.03 g/cm) was added3) After the solution is completely dissolved, 20mg of three-dimensional reduced graphene oxide is placed into the solution, the solution is soaked in a water bath at 10 ℃ for 3 days, then the solution and the three-dimensional reduced graphene oxide are transferred into a plastic beaker, the plastic beaker is frozen and dried at-40 ℃ for 3 days, the obtained solid mixture is pre-decomposed for 2 hours under a high-purity nitrogen atmosphere at 200 ℃ to obtain a reaction precursor, and then the reaction precursor is roasted for 24 hours under a high-purity nitrogen atmosphere at 650 ℃ to obtain the lithium iron phosphate/graphene composite material.
Example 3
The preparation method of the lithium iron phosphate and graphene composite material comprises the following steps:
a hydrothermal process: 5.0g of graphite and 3.75g of NaNO were weighed out separately3Placing into a 1L beaker, stirring with mechanical strength, slowly adding 150mL concentrated sulfuric acid, stirring for 0.5 hr, and slowly adding 20g KMnO4After the addition of the reaction mixture was completed in 0.5 hour, the stirring was stopped after further stirring for 20 hours because of the increase in the viscosity of the reaction mixture, to obtain a paste-like mauve substance. After standing for 5 days, 500mL of deionized water and 30mL of H were slowly added2O2And at the moment, the color of the solution is changed into obvious bright yellow, and after the solution is fully reacted, the solution is centrifuged and washed to obtain the graphite oxide. Dissolving 120mg of graphite oxide in 80mL of deionized water, adding 10mL of concentrated sulfuric acid, performing ultrasonic dispersion for 3 hours, transferring the solution into a small glass bottle, averagely transferring the solution into 5 hydrothermal reaction kettles, reacting in an oven at 200 ℃ for 18 hours, washing, and collecting 24mg of three-dimensionally reduced graphene oxide.
A compounding procedure: dissolving 0.83g of ferrous sulfate, 0.35g of ammonium dihydrogen phosphate, 0.21g of lithium nitrate and 0.21g of hydroxylamine hydrochloride in 12mL of deionized water, after complete dissolution, putting 24mg of three-dimensional reduced graphene oxide into the solution, soaking in a water bath at 20 ℃ for 2 days, then transferring the solution and the three-dimensional reduced graphene oxide into a plastic beaker, freeze-drying at-30 ℃ for 3 days, pre-decomposing the obtained solid mixture at 250 ℃ for 1.5 hours under a high-purity argon atmosphere to obtain a reaction precursor, and then roasting the reaction precursor at 600 ℃ for 24 hours under a high-purity argon atmosphere to obtain the lithium iron phosphate/graphene composite material.
Example 4
The preparation method of the lithium iron phosphate and graphene composite material comprises the following steps:
a hydrothermal process: 5.0g of graphite and 3.75g of NaNO were weighed out separately3Placing into a 1L beaker, stirring with mechanical strength, slowly adding 150mL concentrated sulfuric acid, stirring for 0.5 hr, and slowly adding 20g KMnO4After the addition of the reaction mixture was completed in 0.5 hour, the stirring was stopped after further stirring for 20 hours because of the increase in the viscosity of the reaction mixture, to obtain a paste-like mauve substance. After standing for 5 days, 500mL of deionized water and 30mL of H were slowly added2O2And at the moment, the color of the solution is changed into obvious bright yellow, and after the solution is fully reacted, the solution is centrifuged and washed to obtain the graphite oxide. Dissolving 60mg of graphite oxide in 80mL of deionized water, adding 12mL of concentrated sulfuric acid, performing ultrasonic dispersion for 3 hours, transferring the solution into a small glass bottle, averagely transferring the solution into 5 hydrothermal reaction kettles, reacting in an oven at 200 ℃ for 24 hours, washing, and collecting to obtain 12mg of three-dimensional reduced graphene oxide.
A compounding procedure: 0.72g of ferrous chloride, 0.37g of lithium acetate and 0.64g of ascorbic acid were dissolved in 12mL of deionized water, and 246.07 μ L of concentrated phosphoric acid (ρ ═ 1.69 g/cm) was added3) And after complete dissolution, putting 12mg of three-dimensional reduced graphene oxide into the solution, soaking in a water bath at 25 ℃ for 2 days, then transferring the solution and the three-dimensional reduced graphene oxide into a plastic beaker, freeze-drying at-20 ℃ for 2 days, pre-decomposing the obtained solid mixture for 1 hour at 300 ℃ in a high-purity argon atmosphere to obtain a reaction precursor, and then roasting the reaction precursor for 24 hours at 550 ℃ in a high-purity argon atmosphere to obtain the lithium iron phosphate/graphene composite material.
Example 5
The preparation method of the lithium iron phosphate and graphene composite material comprises the following steps:
a hydrothermal process: 5.0g of graphite and 3.75g of NaNO were weighed out separately3Placing into a 1L beaker, stirring with mechanical strength, slowly adding 150mL concentrated sulfuric acid, stirring for 0.5 hr, and slowly adding 20g KMnO4After the addition of the reaction mixture was completed in 0.5 hour, the stirring was stopped after further stirring for 20 hours because of the increase in the viscosity of the reaction mixture, to obtain a paste-like mauve substance. After standing for 5 days, 500mL of deionized water and 30mL of H were slowly added2O2And at the moment, the color of the solution is changed into obvious bright yellow, and after the solution is fully reacted, the solution is centrifuged and washed to obtain the graphite oxide. Dissolving 90mg of graphite oxide in 80mL of deionized water, adding 12mL of concentrated sulfuric acid, performing ultrasonic dispersion for 3 hours, transferring the solution into a small glass bottle, averagely transferring the solution into 5 hydrothermal reaction kettles, reacting in an oven at 200 ℃ for 18 hours, washing, and collecting 18mg of three-dimensionally reduced graphene oxide.
A compounding procedure: 1.20g of ferrous sulfate, 0.26g of lithium chloride and 0.76g of ascorbic acid were dissolved in 12mL of deionized water, and 295.28 μ L of concentrated phosphoric acid (ρ ═ 1.69 g/cm) was added3) And after complete dissolution, putting 18mg of three-dimensional reduced graphene oxide into the solution, soaking in a water bath at 10 ℃ for 2 days, then transferring the solution and the three-dimensional reduced graphene oxide into a plastic beaker, freeze-drying at-20 ℃ for 2 days, pre-decomposing the obtained solid mixture for 1 hour at 300 ℃ in a high-purity nitrogen atmosphere to obtain a reaction precursor, and then roasting the reaction precursor for 24 hours at 550 ℃ in a nitrogen atmosphere to obtain the lithium iron phosphate/graphene composite material.
Taking the final product of lithium iron phosphate and graphene composite material obtained in the embodiment 4 as a positive electrode material of a lithium ion battery, adopting the lithium iron phosphate and graphene composite material, acetylene black and PVDF with the mass ratio of 85:5:10, and preparing the mixture into uniform slurry by using an N-methylpyrrolidone (NMP) solvent; the slurry was applied to an aluminum foil, which was uniformly applied to a film sheet by a doctor blade, and uniformly adhered to the surface of the copper foil. The prepared coating is placed in a drying oven and dried for 12 hours at the temperature of 110 ℃; after drying, moving the mixture into a vacuum drying oven, and carrying out vacuum drying for 10 hours at 120 ℃; tabletting the dried composite material coating by a tablet machine; cutting electrode plate with mechanical cutting machine, lithium plate as counter electrode, and 1 mol. L electrolyte-1LiPF6Performing charge and discharge performance test by using a battery tester for the/EC + DMC solution to obtain the product lithium iron phosphate and graphene composite materialThe results of the cycle stability test at a current density of 0.1C for the lithium ion battery positive electrode material are shown in fig. 7. As can be seen from FIG. 7, the cycling stability of the battery is good, and the battery capacity is still stabilized at 141.6mAhg after 50 cycles-1。
Claims (16)
1. A preparation method of a lithium iron phosphate/graphene composite material comprises the following steps:
A. dissolving an iron source, a phosphate source, a lithium source and a reducing agent in deionized water, uniformly stirring to obtain a soaking solution, and then dispersing the three-dimensional reduced graphene oxide in the soaking solution to prepare a mixed solution for standing;
B. carrying out vacuum freeze drying on the placed mixed solution until the water is completely sublimated to prepare a solid mixture;
C. pre-decomposing the solid mixture for 1-6 hours at 160-450 ℃ under the inert gas protective atmosphere to obtain a reaction precursor; then roasting the reaction precursor for 24-36 hours at 450-750 ℃ under the protection of inert gas to obtain a lithium iron phosphate/graphene composite material;
in the step A, an iron source is selected from one or more of ferrous chloride, ferrous sulfate, ferrous acetate and ferrous oxalate, and the concentration of iron ions in the iron source in the mixed solution is 0.05-0.80 mol/L;
in the step A, a phosphate radical source is selected from one or more of phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, and the concentration of phosphate radicals in the mixed solution is 0.05-0.80 mol/L;
the lithium source in the step A is one or more selected from lithium chloride, lithium sulfate, lithium nitrate and lithium acetate, and the concentration of lithium ions in the lithium source in the mixed solution is 0.05-0.80 mol/L;
the reducing agent in the step A is selected from one or more of ascorbic acid, hydrazine hydrate and hydroxylamine hydrochloride, and the concentration of the reducing agent in the soaking solution is 0.05-0.80 mol/L.
2. The method of claim 1, wherein: pre-decomposing the solid mixture in the step C for 1-4 hours at 160-300 ℃ under the inert gas protective atmosphere to obtain a reaction precursor; and then roasting the reaction precursor for 24-30 hours at the temperature of 450-600 ℃ in the inert gas protective atmosphere to obtain the lithium iron phosphate/graphene composite material.
3. The method of claim 1, wherein: in the step A, an iron source is ferrous chloride, and the concentration of iron ions in the iron source in the mixed solution is 0.15-0.40 mol/L; in the step A, the phosphate source is phosphoric acid, and the concentration of phosphate in the mixed solution is 0.15-0.40 mol/L; in the step A, the lithium source is lithium chloride, and the concentration of lithium in the mixed solution is 0.15-0.40 mol/L.
4. The method of claim 1, wherein: the mass ratio of iron ions, phosphate radicals and lithium ions in the soaking solution is 1:1: 1.
5. The method of claim 1, wherein: in the step A, the reducing agent is ascorbic acid, and the concentration of the reducing agent in the mixed solution is 0.15-0.40 mol/L.
6. The method of claim 1, wherein: in the step A, the concentration of the three-dimensional reduced graphene oxide in the mixed solution is 0.1-6.0 g/L.
7. The method of claim 6, wherein: in the step A, the concentration of the three-dimensional reduced graphene oxide in the mixed solution is 0.6-3.0 g/L.
8. The method of claim 1, wherein: the placing time in the step A is more than 1 day; and C, when the mixture is placed in the step A, the temperature of the mixture is 3-80 ℃.
9. The method of claim 8, wherein: the standing time in the step A is 1 to 3 days; and C, when the mixture is placed in the step A, the temperature of the mixture is 10-30 ℃.
10. The method of claim 1, wherein: the freeze-drying temperature in the step B is-50-0 ℃; the freeze drying time is more than 2 days; vacuum degree of vacuum freeze drying is less than 50 Pa.
11. The method of claim 10, wherein: the freeze-drying temperature in the step B is between-50 and-20 ℃; the freeze drying time is 2-4 days.
12. The method of claim 1, wherein: and the inert gas in the step C is one or two of nitrogen and argon.
13. The method of claim 12, wherein: and the inert gas in the step C is nitrogen.
14. A lithium iron phosphate/graphene composite material prepared by the method for preparing a lithium iron phosphate/graphene composite material according to claim 1 or 2.
15. A lithium ion battery positive electrode made of the lithium iron phosphate/graphene composite material according to claim 14.
16. A lithium ion battery made comprising the lithium ion battery positive electrode of claim 15.
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| CN106252628A (en) * | 2016-08-30 | 2016-12-21 | 安徽师范大学 | The preparation method of a kind of manganese oxide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery |
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