CN112047321A - Method for preparing composite phosphate lithium battery anode material - Google Patents
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- CN112047321A CN112047321A CN202010944815.0A CN202010944815A CN112047321A CN 112047321 A CN112047321 A CN 112047321A CN 202010944815 A CN202010944815 A CN 202010944815A CN 112047321 A CN112047321 A CN 112047321A
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Abstract
The invention relates to the field of preparation of lithium battery anode materials, in particular to a method for preparing a composite phosphate lithium battery anode material, which comprises the following steps: s1, crushing and drying: loading the X into crushing and drying equipment, adding a certain amount of crushing medium and dispersing agent into the equipment, crushing the X to be nano-scale, and drying to obtain a semi-finished product Q1; s2, raw material preparation: raw materials of a required lithium source, a required TM source, a required phosphorus source and a required doping modification element M are mixed according to a molar ratio of 1.0-1.2: 0.8-1.0: 1.0: weighing 0-0.2, and preparing to obtain a semi-finished product Q2. The method has the advantages of simple process route, no pollution, low raw material cost, short production period and low energy consumption, and can be used for large-scale production; the prepared lithium battery anode has high specific capacity and high compaction density, reduces the internal resistance of the lithium battery, improves the safety, low-temperature and rate charge and discharge performances, and prolongs the cycle life of the lithium battery; the method can be applied to the manufacturing of lithium ion batteries in the fields of traffic, energy storage and the like on a large scale.
Description
Technical Field
The invention relates to the field of preparation of lithium battery anode materials, in particular to a method for preparing a composite phosphate lithium battery anode material.
Background
The human beings continuously increase the protection and improvement of the ecological environment, effectively reduce the dependence on unclean and non-renewable energy sources such as coal, petroleum and the like by optimizing and adjusting the energy structure, and efficiently develop and utilize renewable energy sources such as solar energy, hydroenergy, wind energy, geothermal energy and the like to meet the increasing energy demand. The lithium ion battery is used as an energy storage device for realizing high-efficiency energy storage and energy conversion, an effective path is provided for optimizing and adjusting an energy structure, and the lithium ion battery is widely applied to the fields of communication base stations, wind energy, electric vehicles and the like.
In a lithium ion battery, LiCoO2 has high cost and short resource, has potential safety hazard and can only be applied to the field of consumer markets, and nickel cobalt lithium manganate has high energy density, is already applied to the traffic fields of new energy automobiles and the like on a large scale, but has poor thermal stability, potential safety hazard, short service life and the like; lithium manganate has the advantage of low cost, but has low energy density, serious capacity loss and poor cycle life in a high-temperature environment, and the factors prevent the lithium manganate from being widely applied; lithium iron phosphate has good electrochemical performance and a stable structure in the charging and discharging process, but has the defects of low energy density and poor rate discharging performance and low-temperature performance, so that the development of a method for preparing the composite lithium phosphate battery cathode material is urgently needed.
Disclosure of Invention
The invention aims to provide a method for preparing a composite phosphate lithium battery cathode material, which aims to solve the problems of high cost, resource shortage, potential safety hazard, poor thermal stability of nickel cobalt lithium manganate, low energy density of lithium manganate, serious capacity loss and poor cycle life in a high-temperature environment, low energy density of lithium iron phosphate, and poor rate discharge performance and low-temperature performance of LiCoO2 provided in the background art.
The technical scheme of the invention is as follows: a method for preparing a composite phosphate lithium battery positive electrode material comprises the following steps:
s1, crushing and drying: loading the X into crushing and drying equipment, adding a certain amount of crushing medium and dispersing agent into the equipment, crushing the X to be nano-scale, and drying to obtain a semi-finished product Q1;
s2, raw material preparation: raw materials of a required lithium source, a required TM source, a required phosphorus source and a required doping modification element M are mixed according to a molar ratio of 1.0-1.2: 0.8-1.0: 1.0: weighing 0-0.2, and preparing to obtain a semi-finished product Q2;
s3, mixing, weighing and preparing: mixing Q1 and Q2 according to a molar ratio of 0-0.5: weighing and preparing 0.5-1.0 to obtain a preparation material;
s4, weighing a carbon source: weighing an excessive carbon source to obtain a carbon source material, wherein the carbon source material is used in an amount such that the carbon content in the product is 1-10% by mass;
s5, mixing, crushing and drying: the preparation material and the carbon source material are put into a crushing, mixing and drying device together, a certain amount of mixed medium and a certain amount of dispersing agent are added into the device, the materials are uniformly mixed and crushed to be nano-scale, and the materials are dried to obtain a semi-finished product Q3;
s6, melting and sieving: putting Q3 into a sagger, feeding the sagger into an atmosphere synthesis furnace containing protective gas, decomposing, carbonizing and melting for 2-10 hours, raising the temperature, melting, crystallizing and synthesizing for 3-30 hours, then cooling to room temperature, crushing and sieving, wherein the undersize is the composite phosphate lithium battery positive electrode material (1-Q) Li1+ aTM1-bMbPO 4. qX. C.
Further, in S1, X is an inorganic compound crystal material; c is carbon, the content of wt% is 1-10%, in the S2, TM is transition elements such as Fe, Ni, Co, Mn and V, M is doping elements, and the lithium source is at least one of Li2CO3, LiOH & H2O, LiOH, LiH2PO4, CH3COOLi, Li3PO4, Li2C2O4 and C6H5Li3O7 & 4H 2O.
Further, in S1, the X source is lithium titanate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt manganese zirconate, lithium manganese oxide and lithium nickel manganese oxide, or at least one of carbide, boride, fluoride, sulfide, phosphide, oxide and nitride of the M element in S2.
In S2, TM is a transition element such as Fe, Ni, Co, Mn, V, etc., and the TM source is at least one of TM-containing phosphate, oxalate, acetate, ammonia complex, carbonyl complex, hydroxide, oxide, carbonate, carbide, and nitrate.
Further, in S2, the phosphorus source is at least one of metal-containing phosphate, phosphoric acid, lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, or other phosphate.
In S2, the source of the doping element M is at least one of hydroxides, carbonates, oxides, phosphates, acetates, oxalates, ammonia complexes, and carbonyl complexes of aluminum, cobalt, nickel, manganese, titanium, antimony, magnesium, lithium, bismuth, gallium, tin, tungsten, germanium, tantalum, vanadium, strontium, cesium, indium, zinc, niobium, yttrium, molybdenum, rubidium, zirconium, silicon, boron, and lanthanoids, or at least one of complex hydroxides, complex carbonates, or complex oxides containing the above elements.
In S4, the carbon source is at least one of glucose, sucrose, graphite, polyethylene glycol, polyvinyl alcohol, starch, citric acid, lactose, fructose, carbon nanotubes, carbon nanofibers, graphene, carbon black, phenolic resin, epoxy resin, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, acetylene black, mesophase pitch, and activated carbon.
In S5, the dispersant is at least one of ethanol, propanol, isopropanol, methanol, deionized water, oxalic acid, acetic acid, citric acid, ethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene amine, urea, polyvinyl alcohol, polyacrylamide, acrylic resin, alkylolamide, stearic acid, fatty glyceride, and N-methylpyrrolidone.
In S6, the shielding gas is one or a mixture of two or more of nitrogen, argon, helium, hydrogen, and carbon monoxide.
Further, in the S6, (1-q) Li1+ aTM1-bMbPO 4. qX. C, wherein a is more than or equal to 0 and less than or equal to 0.2, b is more than or equal to 0 and less than 0.2, and q is more than or equal to 0 and less than 0.5, the decomposition, carbonization and melting are carried out within the temperature range of 300-400 ℃, the temperature is raised to 610-850 ℃, the materials are subjected to melt crystallization synthesis, and the materials are crushed and sieved by a 200-mesh sieve.
The invention provides a method for preparing a composite phosphate lithium battery anode material by improvement, which has the following improvement and advantages compared with the prior art:
the invention has simple process route, no pollution, cheap raw materials, short production period and low energy consumption, and can be produced in large scale; the prepared lithium battery anode has high specific capacity and high compaction density, reduces the internal resistance of the lithium battery, improves the safety, low-temperature and rate charge and discharge performances, and prolongs the cycle life of the lithium battery; the lithium ion battery can be applied to the fields of manufacturing traffic (electric automobiles, electric bicycles, electric ships and the like), energy storage (electric tools, communication base stations, wind power generation, solar power stations, power grid peak regulation, valley regulation and the like) and the like on a large scale.
Drawings
The invention is further explained below with reference to the figures and examples:
FIG. 1 is a first schematic flow chart of the method of the present invention;
FIG. 2 is a second schematic flow chart of the method of the present invention;
fig. 3 is a schematic diagram of the performance of the composite phosphate lithium battery positive electrode material of the present invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1 to 3, 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 method for preparing a composite phosphate lithium battery anode material, which comprises the following steps,
s1, crushing and drying: putting X into crushing and drying equipment, wherein X is Co3O4, adding a certain amount of crushing medium and dispersant into the equipment, the using amount of deionized water is 100% of the total mass of Co3O4, and the using amount of polyethylene glycol is 1% of the total mass of Co3O4, crushing the X to a nanometer level, and drying to obtain a semi-finished product Q1;
s2, raw material preparation: raw materials of a required lithium source Li2CO3, a TM source Fe0.99V0.01PO4, a phosphorus source NH4H2PO4 and a doping modification element M source MoO3 are mixed according to a molar ratio of 0.53: 0.99: 0.01: 0.01, weighing and preparing to obtain a semi-finished product Q2;
s3, mixing, weighing and preparing: mixing Q1 and Q2 according to a molar ratio of 0.01: 0.99, weighing and preparing to obtain a preparation material;
s4, weighing a carbon source: then weighing a carbon source, namely glucose monohydrate, wherein the using amount of the carbon source is 10 percent of the total mass of Q2, so as to obtain a carbon source material;
s5, mixing, crushing and drying: the preparation material and the carbon source material are put into a crushing, mixing and drying device together, a certain amount of mixed medium and a certain amount of dispersing agent are added into the device, the amount of deionized water is 100 percent of the total mass of Q2, the dispersing agent is polyethylene glycol, and the amount of polyethylene glycol is 2 percent of the total mass of Q2, the materials are uniformly mixed and crushed to be nano-scale, and the semi-finished product Q3 is obtained after drying;
s6, melting and sieving: putting Q3 into a sagger, feeding into an atmosphere synthesis furnace containing protective gas N2, decomposing, carbonizing and melting for 4 hours at the temperature of 300-350 ℃, then raising the temperature to 780-800 ℃, melting, crystallizing and synthesizing for 10 hours, then cooling to room temperature, crushing and sieving by a 200-mesh sieve, wherein 0.99 Li1.06Fe0.98V0.01Mo0.01PO4.0.01 Co3O 4. C is undersize of the phosphate lithium battery anode material.
Example two
The invention provides a method for preparing a composite phosphate lithium battery anode material, which comprises the following steps,
s1, crushing and drying: putting X into crushing and drying equipment, wherein the X is Li4Ti5O12, adding a certain amount of crushing medium and dispersant into the equipment, the using amount of deionized water is 100% of the total mass of Li4Ti5O12, and the using amount of polyethylene glycol is 1% of the total mass of Li4Ti5O12, crushing the X to a nanometer level, and drying to obtain a semi-finished product Q1;
s2, raw material preparation: raw materials of a required lithium source Li2CO3, a TM source Fe0.99V0.01PO4, a phosphorus source NH4H2PO4 and a doped modified Al source Al2O3 are mixed according to a molar ratio of 0.53: 0.99: 0.01: 0.005 is weighed and prepared to obtain a semi-finished product Q2;
s3, mixing, weighing and preparing: mixing Q1 and Q2 according to a molar ratio of 0.01: 0.99, weighing and preparing to obtain a preparation material;
s4, weighing a carbon source: then weighing carbon sources of glucose monohydrate and acetylene black, wherein the mass ratio of the glucose monohydrate to the acetylene black is 9:1, and the using amount of the carbon sources is 9% of the total mass of Q2, so as to obtain a carbon source material;
s5, mixing, crushing and drying: the preparation material and the carbon source material are put into a crushing, mixing and drying device together, a certain amount of mixed medium and a certain amount of dispersing agent are added into the device, the amount of deionized water is 100 percent of the total mass of Q2, the dispersing agent is polyethylene glycol, and the amount of polyethylene glycol is 2 percent of the total mass of Q2, the materials are uniformly mixed and crushed to be nano-scale, and the semi-finished product Q3 is obtained after drying;
s6, melting and sieving: putting Q3 into a sagger, feeding into an atmosphere synthesis furnace containing protective gas N2, decomposing, carbonizing and melting for 3 hours at the temperature of 340-350 ℃, then raising the temperature to the temperature of 780-790 ℃, carrying out melt crystallization synthesis for 10 hours, then cooling to room temperature, crushing and sieving by a 200-mesh sieve, wherein 0.99 Li1.06Fe0.98Co0.01Al0.01PO4.0.01 Li4Ti5O12 & C which is an undersize product is a synthetic phosphate lithium battery anode material.
EXAMPLE III
The invention provides a method for preparing a composite phosphate lithium battery anode material, which comprises the following steps,
s1, crushing and drying: loading X into crushing and drying equipment, wherein X is LiCoO2, adding a certain amount of crushing medium and dispersing agent into the equipment, the using amount of deionized water is 100% of the total mass of LiCoO2, and the using amount of polyethylene glycol is 1% of the total mass of LiCoO2, crushing the X to a nanometer level, and drying to obtain a semi-finished product Q1;
s2, raw material preparation: raw materials of a required lithium source Li2CO3, a TM source Fe0.99V0.01PO4, a phosphorus source NH4H2PO4 and a doped modification element Zr source ZrO2 are mixed according to a molar ratio of 0.53: 0.99: 0.01: 0.01, weighing and preparing to obtain a semi-finished product Q2;
s3, mixing, weighing and preparing: mixing Q1 and Q2 according to a molar ratio of 0.02: 0.98, weighing and preparing to obtain a preparation material;
s4, weighing a carbon source: weighing carbon source sucrose, wherein the carbon source consumption is 10% of the total mass of Q2, and obtaining carbon source materials;
s5, mixing, crushing and drying: the preparation material and the carbon source material are put into a crushing, mixing and drying device together, a certain amount of mixed medium and a certain amount of dispersing agent are added into the device, the amount of deionized water accounts for 100% of the total mass of Q2, the dispersing agent is polyethylene glycol, and the amount of polyethylene glycol accounts for 3% of the total mass of Q2, the materials are uniformly mixed and crushed to be nano-scale, and the semi-finished product Q3 is obtained after drying;
s6, melting and sieving: putting Q3 into a sagger, feeding into an atmosphere synthesis furnace containing protective gas N2, decomposing, carbonizing and melting for 4 hours at the temperature of 350-360 ℃, then raising the temperature to the temperature of 780-785 ℃, melting, crystallizing and synthesizing for 10 hours, then cooling to room temperature, crushing and sieving by a 200-mesh sieve, and taking 0.98 Li1.06Fe0.98Mn0.01Zr0.01PO4.0.02 LiCoO 2. C as the composite phosphate lithium battery anode material.
Example four
The invention provides a method for preparing a composite phosphate lithium battery anode material, which comprises the following steps,
s1, crushing and drying: putting X into crushing and drying equipment, wherein the X is LiMn2O4, adding a certain amount of crushing medium and dispersing agent into the equipment, the using amount of deionized water is 100% of the total mass of LiMn2O4, and the using amount of polyethylene glycol is 1% of the total mass of LiMn2O4, crushing the X to a nanometer level, and drying to obtain a semi-finished product Q1;
s2, raw material preparation: raw materials of a required lithium source Li2CO3, a TM source Fe0.99V0.01PO4, a phosphorus source NH4H2PO4 and a doped modified element Ti source TiO2 are mixed according to a molar ratio of 0.53: 0.99: 0.01: 0.01, weighing and preparing to obtain a semi-finished product Q2;
s3, mixing, weighing and preparing: mixing Q1 and Q2 according to a molar ratio of 0.02: 0.98, weighing and preparing to obtain a preparation material;
s4, weighing a carbon source: then weighing a carbon source, namely glucose monohydrate and polyethylene glycol, wherein the mass ratio of the glucose monohydrate to the polyethylene glycol is 8:2, and the using amount of the carbon source is 11% of the total mass of Q2, so as to obtain a carbon source material;
s5, mixing, crushing and drying: the preparation material and the carbon source material are put into a crushing, mixing and drying device together, a certain amount of mixed medium and a certain amount of dispersing agent are added into the device, the amount of deionized water is 100 percent of the total mass of Q2, the dispersing agent is polyethylene glycol, and the amount of polyethylene glycol is 2 percent of the total mass of Q2, the materials are uniformly mixed and crushed to be nano-scale, and the semi-finished product Q3 is obtained after drying;
s6, melting and sieving: putting Q3 into a sagger, feeding into an atmosphere synthesis furnace containing protective gas N2, decomposing, carbonizing and melting for 3 hours at the temperature of 370-380 ℃, then raising the temperature to the temperature of 790-795 ℃, melting, crystallizing and synthesizing for 10 hours, then cooling to room temperature, crushing and sieving by a 200-mesh sieve, and taking 0.98 Li1.06Fe0.98Ni0.01Til0.01PO4.0.02 LiMn2O 4. C as the synthetic phosphate lithium battery anode material.
The performance indexes of the composite phosphate lithium battery positive electrode materials prepared in the first to fourth embodiments are as follows:
in the above embodiments of the present invention, the specific capacity of the electrical property obtained in the first embodiment is the highest value, and the highest value reaches 159.4, so the first embodiment is a better preparation method of the composite phosphate lithium battery cathode material, the prepared lithium battery cathode has high specific capacity and large compaction density, the internal resistance of the lithium battery is reduced, the safety, low-temperature and rate charge and discharge performance are improved, and the cycle life of the lithium battery is prolonged.
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. A method for preparing a composite phosphate lithium battery anode material is characterized by comprising the following steps: the method comprises the following steps:
s1, crushing and drying: loading the X into crushing and drying equipment, adding a certain amount of crushing medium and dispersing agent into the equipment, crushing the X to be nano-scale, and drying to obtain a semi-finished product Q1;
s2, raw material preparation: raw materials of a required lithium source, a required TM source, a required phosphorus source and a required doping modification element M are mixed according to a molar ratio of 1.0-1.2: 0.8-1.0: 1.0: weighing 0-0.2, and preparing to obtain a semi-finished product Q2;
s3, mixing, weighing and preparing: mixing Q1 and Q2 according to a molar ratio of 0-0.5: weighing and preparing 0.5-1.0 to obtain a preparation material;
s4, weighing a carbon source: weighing an excessive carbon source to obtain a carbon source material, wherein the carbon source material is used in an amount such that the carbon content in the product is 1-10% by mass;
s5, mixing, crushing and drying: the preparation material and the carbon source material are put into a crushing, mixing and drying device together, a certain amount of mixed medium and a certain amount of dispersing agent are added into the device, the materials are uniformly mixed and crushed to be nano-scale, and the materials are dried to obtain a semi-finished product Q3;
s6, melting and sieving: putting Q3 into a sagger, feeding the sagger into an atmosphere synthesis furnace containing protective gas, decomposing, carbonizing and melting for 2-10 hours, raising the temperature, melting, crystallizing and synthesizing for 3-30 hours, then cooling to room temperature, crushing and sieving, wherein the undersize is the composite phosphate lithium battery positive electrode material (1-Q) Li1+ aTM1-bMbPO 4. qX. C.
2. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in the S1, X is an inorganic compound crystal material; c is carbon, the content of wt% is 1-10%, in the S2, TM is transition elements such as Fe, Ni, Co, Mn and V, M is doping elements, and the lithium source is at least one of Li2CO3, LiOH & H2O, LiOH, LiH2PO4, CH3COOLi, Li3PO4, Li2C2O4 and C6H5Li3O7 & 4H 2O.
3. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in the step S1, the X source is lithium titanate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt manganese zirconate, lithium manganese oxide, and lithium nickel manganese oxide, or at least one of a carbide, a boride, a fluoride, a sulfide, a phosphide, an oxide, and a nitride of the M element in the step S2.
4. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in S2, TM is transition element such as Fe, Ni, Co, Mn, V, etc., and TM source is at least one of phosphate, oxalate, acetate, ammonia coordination compound, carbonyl coordination compound, hydroxide, oxide, carbonate, carbide and nitrate containing TM.
5. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in the step S2, the phosphorus source is at least one of metal-containing phosphate, phosphoric acid, lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, or other phosphate.
6. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in S2, the source of the doping element M is at least one of hydroxides, carbonates, oxides, phosphates, acetates, oxalates, ammonia complexes, and carbonyl complexes of aluminum, cobalt, nickel, manganese, titanium, antimony, magnesium, lithium, bismuth, gallium, tin, tungsten, germanium, tantalum, vanadium, strontium, cesium, indium, zinc, niobium, yttrium, molybdenum, rubidium, zirconium, silicon, boron, and lanthanoids, or at least one of composite hydroxides, composite carbonates, or composite oxides containing the above elements.
7. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in S4, the carbon source is at least one of glucose, sucrose, graphite, polyethylene glycol, polyvinyl alcohol, starch, citric acid, lactose, fructose, carbon nanotubes, carbon nanofibers, graphene, carbon black, phenolic resin, epoxy resin, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, acetylene black, mesophase pitch and activated carbon.
8. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in the step S5, the dispersant is at least one of ethanol, propanol, isopropanol, methanol, deionized water, oxalic acid, acetic acid, citric acid, ethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene amine, urea, polyvinyl alcohol, polyacrylamide, acrylic resin, alkylolamide, stearic acid, fatty glyceride, N-methylpyrrolidone, and the like.
9. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in the step S6, the protective gas is one or a mixture of more than two of five gases of nitrogen, argon, helium, hydrogen and carbon monoxide.
10. The method for preparing the positive electrode material for the composite phosphate lithium battery as claimed in claim 1, wherein: in the S6, (1-q) Li1+ aTM1-bMbPO 4. qX. C, wherein a is more than or equal to 0 and less than or equal to 0.2, b is more than or equal to 0 and less than 0.2, and q is more than or equal to 0 and less than 0.5, the decomposition, carbonization and melting are carried out within the temperature range of 300-400 ℃, the temperature is raised to 610-850 ℃, the materials are subjected to melting crystallization synthesis, and the materials are crushed and sieved by a 200-mesh sieve.
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