CN114291802A - Preparation and application of MOFs material modified lithium iron phosphate positive electrode material - Google Patents
Preparation and application of MOFs material modified lithium iron phosphate positive electrode material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 58
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 title claims description 38
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 34
- 238000005303 weighing Methods 0.000 claims abstract description 28
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- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
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- 239000010405 anode material Substances 0.000 claims abstract description 22
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- 238000000576 coating method Methods 0.000 claims abstract description 10
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- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 25
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 23
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 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 20
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 16
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- 239000012300 argon atmosphere Substances 0.000 claims description 15
- 239000013110 organic ligand Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 10
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- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
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- 229910021645 metal ion Inorganic materials 0.000 claims description 5
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000001338 self-assembly Methods 0.000 claims description 5
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- 230000009286 beneficial effect Effects 0.000 abstract 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 2
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- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 208000012266 Needlestick injury Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention relates to the technical field of preparation of lithium iron phosphate anode materials, in particular to preparation and application of a MOFs material modified lithium iron phosphate anode material, which comprises the following steps: s1, weighing; s2, preparing an MOFs solution; s3, preparing a polymer solution; s4, spraying; s5, drying, stamping and weighing, wherein the preparation of the LiFePO4 comprises the following steps: a1, configuration; a2, fully stirring; a3, cooling; a4, obtaining the LiFePO4 material. The invention has the beneficial effects that the MOFs porous material coating is coated on the lithium iron phosphate anode material, so that the porous material is hydrolyzed and collapsed by the solvent when the lithium ion battery is heated to a certain temperature, and the polymer in the porous material can automatically melt and close pores, thereby fully blocking the reaction of the anode material and the cathode material and the electrolyte, preventing the occurrence and continuous deterioration of the heat generation reaction in the lithium ion battery, improving the safety of the battery, preventing the damage of solvated lithium ions to the cathode material, and further improving the capacity and the cycle life of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of preparation of lithium iron phosphate anode materials, in particular to preparation and application of a MOFs material modified lithium iron phosphate anode material.
Background
The olivine-structured LiFePO4, as a novel positive electrode material of a healthy ion battery, has the advantages of wide material source, low price, high theoretical specific capacity (about 170 mAh/g), good thermal stability, no hygroscopicity, environmental friendliness and the like, draws wide attention in recent years, and is expected to become a first-choice substitute for LiCoO2But also to a positive electrode material for an ion secondary battery.
Chinese patent No. CN107611413B provides a preparation method of a titanium-doped lithium iron phosphate anode material, which comprises the steps of taking a lithium source compound, a phosphorus source compound, an iron source compound and metallic titanium as raw materials, uniformly mixing, carrying out high-temperature melting in a smelting furnace, carrying out water quenching to obtain particles, grinding and dispersing the particles together with a carbon source compound to enable the particle size to reach a fineness index that D90 is less than or equal to 0.2 mu m, carrying out spray drying to prepare powder, calcining for 40-300 minutes in an atmosphere furnace at 600-800 ℃, and cooling to obtain the lithium iron phosphate anode material; the uniformity of the lithium iron phosphate anode material is improved by adopting a high-temperature melting method; introducing metal titanium powder, reducing Fe3+ in the molten liquid into Fe2+ under a high-temperature molten state, doping the generated Ti4+ into a lithium iron phosphate structure, and improving the electron conductivity of the lithium iron phosphate anode material by forming vacancies; the specific surface area is reduced by grinding, dispersing and carbon coating, and the tap density of the lithium iron phosphate anode material is improved.
The safety problem of the existing lithium ion battery is mainly caused by thermal runaway of the battery, and the internal temperature of the battery is continuously increased due to short circuit caused by abnormal heat generation reaction, overcharge and mutual contact of positive and negative electrode materials, so that more heat generation side reactions are caused, the battery is ignited and even explodes, and the life and property safety of a user is seriously threatened. In order to meet the requirements of electric automobiles on the safety performance of power batteries and the like, at present, a polymer which is molten at a specific temperature is coated on a diaphragm, and a lithium ion conduction channel between an anode and a cathode in a battery is blocked by utilizing the melting of the polymer, so that the aggravation of thermal runaway of the battery is avoided, the short circuit is further stopped or prevented, and the safety of the lithium ion battery is further improved. Although the thermal runaway reaction of the battery can be partially restrained, the lithium ion battery electrodes are usually porous electrodes, and the electrolyte is filled in abundant electrode gaps; the lithium ion conduction between the positive electrode and the negative electrode is blocked, but the reaction of the active substance in the electrode and the electrolyte is still continued, the occurrence and the continuous deterioration of the heat generation reaction in the lithium ion battery cannot be completely prevented from the source, and the thermal runaway reaction caused by heat accumulation can be further caused, so that the lithium ion battery is more easily subjected to spontaneous combustion or explosion in a certain period of time, and the improvement effect is limited. Therefore, the development of the preparation and application of the MOFs material modified lithium iron phosphate cathode material is urgently needed.
Disclosure of Invention
The invention aims to provide preparation and application of a MOFs material modified lithium iron phosphate positive electrode material, and aims to solve the problems that the safety performance of the lithium iron phosphate positive electrode material is poor when the lithium iron phosphate positive electrode material is assembled into a battery, and the capacity and the cycle performance of the lithium ion battery of the lithium iron phosphate positive electrode material are poor.
The technical scheme of the invention is as follows: a preparation method of a MOFs material modified lithium iron phosphate positive electrode material comprises the following steps:
s1, weighing: firstly, 19mg to 25mg NiCl 6H2O and 20 mg to 30mg CoCl 6H2O are weighed and dissolved in 10mL to 30mLNMP, and are mixed evenly by ultrasound to prepare metal precursor solution, and in addition, 250 mg of 350mg of 2-amino terephthalic acid is weighed and dissolved in 10mL to 30mLNMP to be mixed evenly to prepare organic ligand solution;
s2, preparing MOFs solution: gradually adding the organic ligand solution into the metal precursor solution under the condition of stirring, and stirring for 2h-3h to obtain an MOFs solution;
s3, preparing a polymer solution: adding 50ml of NMP into a reaction vessel, stirring at 140 ℃, and adding PVDF and acetylene black to prepare a polymer solution;
s4, spraying: slowly adding the polymer solution into the MOFs solution, continuously heating and stirring for 10 hours to obtain an MOFs-polymer composite solution, and spraying the material on the prepared lithium iron phosphate positive electrode material;
s5, drying, stamping and weighing: and then, putting the coated pole pieces in a vacuum drying oven at 80 ℃ for drying at night, punching the materials into circular pole pieces with the diameter of 14mm by using a punching machine, and weighing and recording the mass of active substances contained in each pole piece.
Further, in the S4, an active material (LiFePO 4): polyvinylidene fluoride (PVDF): mass ratio of acetylene black (C = 8: 1: 1, fully grinding for 1h, grinding the material to be slurry, and uniformly coating the material on the smooth surface of the aluminum foil by using an applicator to form a uniform thin sheet.
Further, in S4, the Metal Organic Frameworks (MOFs) are a class of crystalline porous materials with periodic network structure, especially organic porous materials, formed by connecting inorganic metal centers (metal ions or metal clusters) and bridging organic ligands through self-assembly, which are different from inorganic porous materials and common organic complexes, and have both the rigidity of inorganic materials and the flexibility of organic materials.
Further, the preparation of the LiFePO4 comprises the following steps:
a1, configuration: respectively preparing 0.5mol/L Fe (NO 3) 3.9H 2O solution and NH4H2PO4 solution, and slowly dripping the NH4H2PO4 solution into the Fe (NO 3) 3.9H 2O solution under the stirring condition;
a2, stirring fully: after fully stirring, slowly dropwise adding ammonia water (1 mol/L) into the solution, adjusting the pH of the solution to be =10, stirring for 1 hour again, and transferring the mixed solution into a 200ml reaction kettle lined with polytetrafluoroethylene;
a3, cooling: after the temperature of the reaction kettle is cooled to room temperature, carrying out suction filtration on a reaction product, respectively washing the reaction product with deionized water and absolute ethyl alcohol for three times, and finally putting the reaction product into a vacuum drying oven for drying treatment to obtain a FePO4 precursor;
a4, obtaining LiFePO4 material: the method comprises the following steps of (1) precursor according to molar ratio: lithium source = 1: 1, respectively weighing 0.5g of FePO4 precursor, 0.1391g of LiOH2O and 0.0639g of ascorbic acid, adding a few drops of absolute ethyl alcohol, fully and uniformly grinding in an agate mortar, putting into a porcelain boat, pre-calcining for 5 hours in a tubular furnace in argon atmosphere at 350 ℃, and cooling to room temperature in the tubular furnace to obtain the LiFePO4 material.
Further, in the A4, 0.0639g of ascorbic acid was 10w% of the total mass of LiOHH2O and FePO4, and a temperature rise rate of 5C/min was used at 350 ℃ in a tube furnace under an argon atmosphere.
Further, in the A2, the temperature of an oven in a reaction kettle is set to be 150 ℃, the hydrothermal reaction is carried out for 10 hours, and in the A3, the reaction product after being cleaned is dried in a vacuum drying oven for 24 hours at 80 ℃.
Furthermore, the electrochemical reaction of the lithium iron phosphate positive electrode material in the charging and discharging process mainly comprises two phases: LiFePO4 and FePO4, the reaction process equation:
charging reaction: LiFePO4-xLi + -xe- - = xFePO4+ (1-x) LiFePO4
Discharging reaction: FePO4+ xLi + + xe "= xLiFePO4+ (1-x) FePO 4.
Further, the reaction of the lithium iron phosphate anode material is converted back and forth between FePO4 and LiFePO4 in the charging and discharging processes, when the lithium iron phosphate anode material is in a charging state, Li < + > is removed from the LiFePO4 anode material, migrates through an electrolyte and a diaphragm and is embedded into the anode material, Fe2 < + > loses one electron, the lithium ion and the electron reach the anode from a lead of an external circuit, and the LiFePO4 is converted into FePO 4.
Further, when the lithium iron phosphate positive electrode material is in a discharge state, on the contrary, Li + on the negative electrode is separated and transferred to the positive electrode, meanwhile, electrons are also directionally moved to the positive electrode to form current, and the current is supplied to an electric appliance, so that the FePO4 is changed into LiFePO4 again.
An application of MOFs material modified lithium iron phosphate positive electrode material takes a metal lithium sheet as a negative electrode, a microporous polypropylene membrane of Celgard2400 as a diaphragm, and the concentration of the lithium iron phosphate positive electrode material is 1mol L LiPF6/EC + DMC + EMCQ: 1: 1 volume ratio) as an electrolyte, then assembling the mixed solution into a CR2016 type button cell in a glove box in an argon atmosphere, wherein the environment in the glove box requires that the oxygen pressure is less than 10ppm and the relative humidity is less than 5%, and finally standing the assembled button cell for 12h and then carrying out charge-discharge, alternating current impedance and cyclic voltammetry tests.
The invention provides a preparation method and application of a MOFs material modified lithium iron phosphate positive electrode material through improvement, compared with the prior art, the invention has the following improvements and advantages:
(1) by coating a layer of MOFs porous material coating on the lithium iron phosphate positive electrode material, the porous material is hydrolyzed and collapsed by a solvent under the action of the solvent when the temperature of the lithium ion battery rises to a certain temperature, and a polymer in the porous material can automatically melt and close pores, so that the reaction of the positive electrode material and the negative electrode material with an electrolyte can be fully blocked, the occurrence and continuous deterioration of a heat generation reaction in the lithium ion battery are prevented, and the safety of the battery is improved.
(2) Through the arranged MOFs porous material, when the lithium ion battery works normally, the unique pore diameter structure of the porous material can allow lithium ions to be inserted and extracted through the coating, can also prevent solvated lithium ions from being inserted into the negative electrode material, and can prevent the solvated lithium ions from damaging the negative electrode material, so that the capacity and the cycle life of the lithium ion battery are improved.
Drawings
The invention is further explained below with reference to the figures and examples:
fig. 1 is a flow chart of the preparation of a lithium iron phosphate positive electrode material of the present invention;
fig. 2 is a flow chart of the preparation of LiFePO4 according to the invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1 to 2, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The invention provides a preparation method of a MOFs material modified lithium iron phosphate positive electrode material through improvement, as shown in figures 1-2, the preparation method comprises the following steps:
s1, weighing: firstly, weighing 25mgNiCl 6H2O and 30mgCoCl 6H2O, dissolving in 130mLNMP, ultrasonically mixing uniformly to prepare a metal precursor solution, and weighing 350mg 2-amino terephthalic acid, dissolving in 30mLNMP, mixing uniformly to prepare an organic ligand solution;
s2, preparing MOFs solution: gradually adding the organic ligand solution into the metal precursor solution under the condition of stirring, and stirring for 3 hours to obtain an MOFs solution;
s3, preparing a polymer solution: adding 50ml of NMP (N-methyl-2-pyrrolidone) into a reaction vessel, stirring at 140 ℃, adding PVDF (molecular weight is 30 ten thousand) and acetylene black, and preparing into a polymer solution;
s4, spraying: slowly adding a polymer solution into an MOFs solution, wherein a Metal Organic Framework (MOFs) is formed by connecting an inorganic metal center (metal ions or metal clusters) and a bridged organic ligand through self-assembly, and is a crystalline porous material with a periodic network structure, particularly an organic porous material which is different from an inorganic porous material and an organic complex and has the characteristics of both the rigidity of the inorganic material and the flexibility of the organic material, continuously heating and stirring for 10 hours to obtain the MOFs-polymer composite solution, spraying the material on a prepared lithium iron phosphate positive electrode material, and adding an active substance (LiFePO 4): polyvinylidene fluoride (PVDF): mass ratio of acetylene black (C = 8: 1: 1, fully grinding for 1 hour, grinding the material into slurry, and uniformly coating the material on the surface of a smooth aluminum foil by using a coater to form a uniform sheet;
s5, drying, stamping and weighing: and then, putting the coated pole pieces in a vacuum drying oven at 80 ℃ for drying at night, punching the materials into circular pole pieces with the diameter of 14mm by using a punching machine, and weighing and recording the mass of active substances contained in each pole piece.
Further, the preparation of LiFePO4 comprises the following steps:
a1, configuration: respectively preparing 0.5mol/L Fe (NO 3) 3.9H 2O solution and NH4H2PO4 solution, and slowly dripping the NH4H2PO4 solution into the Fe (NO 3) 3.9H 2O solution under the stirring condition;
a2, stirring fully: after fully stirring, slowly dropwise adding ammonia water (1 mol/L) into the solution, adjusting the pH of the solution to be =10, stirring for 1h again, transferring the mixed solution into a 200ml reaction kettle lined with polytetrafluoroethylene, setting the temperature of an oven in the reaction kettle to be 150 ℃, and carrying out hydrothermal reaction for 10 h;
a3, cooling: after the temperature of the reaction kettle is cooled to room temperature, carrying out suction filtration on a reaction product, respectively washing the reaction product with deionized water and absolute ethyl alcohol for three times, finally putting the reaction product into a vacuum drying oven for drying treatment to obtain a FePO4 precursor, and drying the washed reaction product in the vacuum drying oven for 24 hours at the temperature of 80 ℃;
a4, obtaining LiFePO4 material: the method comprises the following steps of (1) precursor according to molar ratio: lithium source = 1: 1, respectively weighing 0.5g of FePO4 precursor, 0.1391g of LiOH2O and 0.0639g of ascorbic acid, 0.0639g of ascorbic acid being 10w% of the total mass of LiOH2O and FePO4, adding a few drops of absolute ethyl alcohol at a heating rate of 5C/min at 350 ℃ in a tubular furnace in an argon atmosphere, fully and uniformly grinding the mixture in an agate mortar, placing the mixture into a ceramic boat, pre-calcining the mixture for 5 hours at 350 ℃ in the tubular furnace in the argon atmosphere, and cooling the tubular furnace to room temperature to obtain the LiFePO4 material.
An application of a MOFs material modified lithium iron phosphate positive electrode material adopts MOFs: mass ratio of LiFePO4 = 1: 20, taking a metal lithium sheet as a negative electrode, taking a microporous polypropylene membrane of Celgard2400 as a diaphragm, and taking a lithium ion battery with a concentration of 1mol L, wherein the ratio of LiPF6/EC + DMC + EMCQ: 1: 1 volume ratio) as an electrolyte, then assembling the mixed solution into a CR2016 type button cell in a glove box in an argon atmosphere, wherein the environment in the glove box requires that the oxygen pressure is less than 10ppm and the relative humidity is less than 5%, and finally standing the assembled button cell for 12h and then carrying out charge-discharge, alternating current impedance and cyclic voltammetry tests.
Example two
A preparation method of a MOFs material modified lithium iron phosphate positive electrode material comprises the following steps:
s1, weighing: firstly, weighing 25mgNiCl 6H2O and 30mgCoCl 6H2O, dissolving in 130mLNMP, ultrasonically mixing uniformly to prepare a metal precursor solution, and weighing 350mg 2-amino terephthalic acid, dissolving in 30mLNMP, mixing uniformly to prepare an organic ligand solution;
s2, preparing MOFs solution: gradually adding the organic ligand solution into the metal precursor solution under the condition of stirring, and stirring for 3 hours to obtain an MOFs solution;
s3, preparing a polymer solution: adding 50ml of NMP (N-methyl-2-pyrrolidone) into a reaction vessel, stirring at 140 ℃, adding PVDF (molecular weight is 30 ten thousand) and acetylene black, and preparing into a polymer solution;
s4, spraying: slowly adding a polymer solution into an MOFs solution, wherein a Metal Organic Framework (MOFs) is formed by connecting an inorganic metal center (metal ions or metal clusters) and a bridged organic ligand through self-assembly, and is a crystalline porous material with a periodic network structure, particularly an organic porous material which is different from an inorganic porous material and an organic complex and has the characteristics of both the rigidity of the inorganic material and the flexibility of the organic material, continuously heating and stirring for 10 hours to obtain the MOFs-polymer composite solution, spraying the material on a prepared lithium iron phosphate positive electrode material, and adding an active substance (LiFePO 4): polyvinylidene fluoride (PVDF): mass ratio of acetylene black (C = 8: 1: 1, fully grinding for 1 hour, grinding the material into slurry, and uniformly coating the material on the surface of a smooth aluminum foil by using a coater to form a uniform sheet;
s5, drying, stamping and weighing: and then, putting the coated pole pieces in a vacuum drying oven at 80 ℃ for drying at night, punching the materials into circular pole pieces with the diameter of 14mm by using a punching machine, and weighing and recording the mass of active substances contained in each pole piece.
Further, the preparation of LiFePO4 comprises the following steps:
a1, configuration: respectively preparing 0.5mol/L Fe (NO 3) 3.9H 2O solution and NH4H2PO4 solution, and slowly dripping the NH4H2PO4 solution into the Fe (NO 3) 3.9H 2O solution under the stirring condition;
a2, stirring fully: after fully stirring, slowly dropwise adding ammonia water (1 mol/L) into the solution, adjusting the pH of the solution to be =10, stirring for 1h again, transferring the mixed solution into a 200ml reaction kettle lined with polytetrafluoroethylene, setting the temperature of an oven in the reaction kettle to be 150 ℃, and carrying out hydrothermal reaction for 10 h;
a3, cooling: after the temperature of the reaction kettle is cooled to room temperature, carrying out suction filtration on a reaction product, respectively washing the reaction product with deionized water and absolute ethyl alcohol for three times, finally putting the reaction product into a vacuum drying oven for drying treatment to obtain a FePO4 precursor, and drying the washed reaction product in the vacuum drying oven for 24 hours at the temperature of 80 ℃;
a4, obtaining LiFePO4 material: the method comprises the following steps of (1) precursor according to molar ratio: lithium source = 1: 1, respectively weighing 0.5g of FePO4 precursor, 0.1391g of LiOH2O and 0.0639g of ascorbic acid, 0.0639g of ascorbic acid being 10w% of the total mass of LiOH2O and FePO4, adding a few drops of absolute ethyl alcohol at a heating rate of 5C/min at 350 ℃ in a tubular furnace in an argon atmosphere, fully and uniformly grinding the mixture in an agate mortar, placing the mixture into a ceramic boat, pre-calcining the mixture for 5 hours at 350 ℃ in the tubular furnace in the argon atmosphere, and cooling the tubular furnace to room temperature to obtain the LiFePO4 material.
An application of a MOFs material modified lithium iron phosphate positive electrode material adopts MOFs: mass ratio of LiFePO4 = 1: 18, taking a metal lithium sheet as a negative electrode, taking a microporous polypropylene membrane of Celgard2400 as a diaphragm, and taking a lithium ion battery with a concentration of 1mol L, wherein the ratio of LiPF6/EC + DMC + EMCQ: 1: 1 volume ratio) as an electrolyte, then assembling the mixed solution into a CR2016 type button cell in a glove box in an argon atmosphere, wherein the environment in the glove box requires that the oxygen pressure is less than 10ppm and the relative humidity is less than 5%, and finally standing the assembled button cell for 12h and then carrying out charge-discharge, alternating current impedance and cyclic voltammetry tests.
EXAMPLE III
A preparation method of a MOFs material modified lithium iron phosphate positive electrode material comprises the following steps:
s1, weighing: firstly, weighing 25mgNiCl 6H2O and 30mgCoCl 6H2O, dissolving in 130mLNMP, ultrasonically mixing uniformly to prepare a metal precursor solution, and weighing 350mg 2-amino terephthalic acid, dissolving in 30mLNMP, mixing uniformly to prepare an organic ligand solution;
s2, preparing MOFs solution: gradually adding the organic ligand solution into the metal precursor solution under the condition of stirring, and stirring for 3 hours to obtain an MOFs solution;
s3, preparing a polymer solution: adding 50ml of NMP (N-methyl-2-pyrrolidone) into a reaction vessel, stirring at 140 ℃, adding PVDF (molecular weight is 30 ten thousand) and acetylene black, and preparing into a polymer solution;
s4, spraying: slowly adding a polymer solution into an MOFs solution, wherein a Metal Organic Framework (MOFs) is formed by connecting an inorganic metal center (metal ions or metal clusters) and a bridged organic ligand through self-assembly, and is a crystalline porous material with a periodic network structure, particularly an organic porous material which is different from an inorganic porous material and an organic complex and has the characteristics of both the rigidity of the inorganic material and the flexibility of the organic material, continuously heating and stirring for 10 hours to obtain the MOFs-polymer composite solution, spraying the material on a prepared lithium iron phosphate positive electrode material, and adding an active substance (LiFePO 4): polyvinylidene fluoride (PVDF): mass ratio of acetylene black (C = 8: 1: 1, fully grinding for 1 hour, grinding the material into slurry, and uniformly coating the material on the surface of a smooth aluminum foil by using a coater to form a uniform sheet;
s5, drying, stamping and weighing: and then, putting the coated pole pieces in a vacuum drying oven at 80 ℃ for drying at night, punching the materials into circular pole pieces with the diameter of 14mm by using a punching machine, and weighing and recording the mass of active substances contained in each pole piece.
Further, the preparation of LiFePO4 comprises the following steps:
a1, configuration: respectively preparing 0.5mol/L Fe (NO 3) 3.9H 2O solution and NH4H2PO4 solution, and slowly dripping the NH4H2PO4 solution into the Fe (NO 3) 3.9H 2O solution under the stirring condition;
a2, stirring fully: after fully stirring, slowly dropwise adding ammonia water (1 mol/L) into the solution, adjusting the pH of the solution to be =10, stirring for 1h again, transferring the mixed solution into a 200ml reaction kettle lined with polytetrafluoroethylene, setting the temperature of an oven in the reaction kettle to be 150 ℃, and carrying out hydrothermal reaction for 10 h;
a3, cooling: after the temperature of the reaction kettle is cooled to room temperature, carrying out suction filtration on a reaction product, respectively washing the reaction product with deionized water and absolute ethyl alcohol for three times, finally putting the reaction product into a vacuum drying oven for drying treatment to obtain a FePO4 precursor, and drying the washed reaction product in the vacuum drying oven for 24 hours at the temperature of 80 ℃;
a4, obtaining LiFePO4 material: the method comprises the following steps of (1) precursor according to molar ratio: lithium source = 1: 1, respectively weighing 0.5g of FePO4 precursor, 0.1391g of LiOH2O and 0.0639g of ascorbic acid, 0.0639g of ascorbic acid being 10w% of the total mass of LiOH2O and FePO4, adding a few drops of absolute ethyl alcohol at a heating rate of 5C/min at 350 ℃ in a tubular furnace in an argon atmosphere, fully and uniformly grinding the mixture in an agate mortar, placing the mixture into a ceramic boat, pre-calcining the mixture for 5 hours at 350 ℃ in the tubular furnace in the argon atmosphere, and cooling the tubular furnace to room temperature to obtain the LiFePO4 material.
An application of a MOFs material modified lithium iron phosphate positive electrode material adopts MOFs: mass ratio of LiFePO4 = 1: and 15, taking a metal lithium sheet as a negative electrode, taking a microporous polypropylene membrane of Celgard2400 as a diaphragm, and taking the lithium metal sheet as a negative electrode, wherein the concentration of the lithium metal sheet is 1mol L, and the ratio of LiPF6/EC + DMC + EMCQ: 1: 1 volume ratio) as an electrolyte, then assembling the mixed solution into a CR2016 type button cell in a glove box in an argon atmosphere, wherein the environment in the glove box requires that the oxygen pressure is less than 10ppm and the relative humidity is less than 5%, and finally standing the assembled button cell for 12h and then carrying out charge-discharge, alternating current impedance and cyclic voltammetry tests.
Comparative example 1
A pure lithium iron phosphate lithium ion battery that has not been modified.
Correlation performance comparison of lithium iron phosphate lithium ion battery modified by MOFs material
| Experimental number | 1C specific discharge capacity/mAh/g | Capacity retention at 50 weeks/%) | Needle stick test |
| Example one | 130 | 82.6 | No combustion, no fire and no smoke |
| Example two | 135 | 84.5 | No combustion, no fire and no smoke |
| EXAMPLE III | 145 | 85.3 | No combustion, no fire and no smoke |
| Comparative example 1 | 120 | 80.5 | Burning of |
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the MOFs material modified lithium iron phosphate anode material is characterized by comprising the following steps of: the method comprises the following steps:
s1, weighing: firstly, 19mg to 25mg NiCl 6H2O and 20 mg to 30mg CoCl 6H2O are weighed and dissolved in 10mL to 30mLNMP, and are mixed evenly by ultrasound to prepare metal precursor solution, and in addition, 250 mg of 350mg of 2-amino terephthalic acid is weighed and dissolved in 10mL to 30mLNMP to be mixed evenly to prepare organic ligand solution;
s2, preparing MOFs solution: gradually adding the organic ligand solution into the metal precursor solution under the condition of stirring, and stirring for 2h-3h to obtain an MOFs solution;
s3, preparing a polymer solution: adding 50ml of NMP into a reaction vessel, stirring at 140 ℃, and adding PVDF and acetylene black to prepare a polymer solution;
s4, spraying: slowly adding the polymer solution into the MOFs solution, continuously heating and stirring for 10 hours to obtain an MOFs-polymer composite solution, and spraying the material on the prepared lithium iron phosphate positive electrode material;
s5, drying, stamping and weighing: and then, putting the coated pole pieces in a vacuum drying oven at 80 ℃ for drying at night, punching the materials into circular pole pieces with the diameter of 14mm by using a punching machine, and weighing and recording the mass of active substances contained in each pole piece.
2. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 1, wherein the preparation method comprises the following steps: in S4, the active material (LiFePO 4): polyvinylidene fluoride (PVDF): mass ratio of acetylene black (C = 8: 1: 1, fully grinding for 1h, grinding the material to be slurry, and uniformly coating the material on the smooth surface of the aluminum foil by using an applicator to form a uniform thin sheet.
3. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 1, wherein the preparation method comprises the following steps: in S4, the metal-organic frameworks (MOFs) are crystalline porous materials with periodic network structure formed by connecting inorganic metal centers (metal ions or metal clusters) and bridged organic ligands by self-assembly, especially organic porous materials, which are different from inorganic porous materials and common organic complexes, and have the rigidity of inorganic materials and the flexibility of organic materials.
4. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 1, wherein the preparation method comprises the following steps: the preparation of the LiFePO4 comprises the following steps:
a1, configuration: respectively preparing 0.5mol/L Fe (NO 3) 3.9H 2O solution and NH4H2PO4 solution, and slowly dripping the NH4H2PO4 solution into the Fe (NO 3) 3.9H 2O solution under the stirring condition;
a2, stirring fully: after fully stirring, slowly dropwise adding ammonia water (1 mol/L) into the solution, adjusting the pH of the solution to be =10, stirring for 1 hour again, and transferring the mixed solution into a 200ml reaction kettle lined with polytetrafluoroethylene;
a3, cooling: after the temperature of the reaction kettle is cooled to room temperature, carrying out suction filtration on a reaction product, respectively washing the reaction product with deionized water and absolute ethyl alcohol for three times, and finally putting the reaction product into a vacuum drying oven for drying treatment to obtain a FePO4 precursor;
a4, obtaining LiFePO4 material: the method comprises the following steps of (1) precursor according to molar ratio: lithium source = 1: 1, respectively weighing 0.5g of FePO4 precursor, 0.1391g of LiOH2O and 0.0639g of ascorbic acid, adding a few drops of absolute ethyl alcohol, fully and uniformly grinding in an agate mortar, putting into a porcelain boat, pre-calcining for 5 hours in a tubular furnace in argon atmosphere at 350 ℃, and cooling to room temperature in the tubular furnace to obtain the LiFePO4 material.
5. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 4, wherein the preparation method comprises the following steps: in the A4, 0.0639g of ascorbic acid was 10w% of the total mass of LiOHH2O and FePO4, and a temperature rise rate of 5C/min was used at 350 ℃ in a tube furnace under an argon atmosphere.
6. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 4, wherein the preparation method comprises the following steps: in the A2, the temperature of an oven in a reaction kettle is set to be 150 ℃, the hydrothermal reaction is carried out for 10 hours, and in the A3, the cleaned reaction product is dried in a vacuum drying oven for 24 hours at the temperature of 80 ℃.
7. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 4, wherein the preparation method comprises the following steps: the electrochemical reaction of the lithium iron phosphate anode material in the charging and discharging process mainly comprises two phases: LiFePO4 and FePO4, the reaction process equation:
charging reaction: LiFePO4-xLi + -xe- - = xFePO4+ (1-x) LiFePO4
Discharging reaction: FePO4+ xLi + + xe "= xLiFePO4+ (1-x) FePO 4.
8. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 4, wherein the preparation method comprises the following steps: the reaction of the lithium iron phosphate anode material is converted back and forth between FePO4 and LiFePO4 in the charging and discharging processes, when the lithium iron phosphate anode material is in a charging state, Li < + > is separated from the LiFePO4 anode material, migrates through an electrolyte and a diaphragm and is embedded into the anode material, Fe2 < + > loses one electron, the lithium ion and the electron reach the anode from a lead of an external circuit, and the LiFePO4 is converted into FePO 4.
9. The preparation method of the MOFs material modified lithium iron phosphate positive electrode material according to claim 4, wherein the preparation method comprises the following steps: when the lithium iron phosphate anode material is in a discharge state, on the contrary, Li < + > on the cathode can be separated and transferred to the anode, meanwhile, electrons can also be directionally moved to the anode to form current, the current is supplied to an electric appliance, and FePO4 becomes LiFePO4 again.
10. The application of the MOFs material modified lithium iron phosphate positive electrode material is characterized in that: taking a metal lithium sheet as a negative electrode, taking a microporous polypropylene membrane of Celgard2400 as a diaphragm, and taking the lithium sheet as a negative electrode, wherein the concentration of the lithium sheet is 1mol L, and the lithium sheet is LiPF6/EC + DMC + EMCQ: 1: 1 volume ratio) as an electrolyte, then assembling the mixed solution into a CR2016 type button cell in a glove box in an argon atmosphere, wherein the environment in the glove box requires that the oxygen pressure is less than 10ppm and the relative humidity is less than 5%, and finally standing the assembled button cell for 12h and then carrying out charge-discharge, alternating current impedance and cyclic voltammetry tests.
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