CN108878849B - Synthesis process of lithium-rich oxide and lithium ion battery containing lithium-rich oxide - Google Patents

Synthesis process of lithium-rich oxide and lithium ion battery containing lithium-rich oxide Download PDF

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CN108878849B
CN108878849B CN201810725733.XA CN201810725733A CN108878849B CN 108878849 B CN108878849 B CN 108878849B CN 201810725733 A CN201810725733 A CN 201810725733A CN 108878849 B CN108878849 B CN 108878849B
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rich oxide
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CN108878849A (en
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陈伟
王海文
范进雷
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Jiangxi Zhongqi Ruihua New Energy Technology Co ltd
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Jiangxi Zhongqi Ruihua New Energy Technology Co ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a synthesis process of a lithium-rich oxide, and a lithium ion battery containing the lithium-rich oxide, wherein the specific synthesis process of the lithium-rich oxide is as follows: weighing a lithium source and an iron source with a proper molar ratio, dispersing the lithium source and the iron source in deionized water, and after the lithium source and the iron source are completely dissolved, weighing a proper amount of organic carbon source and adding the organic carbon source into the solution; stirring the solution at 80 ℃ until a sol is formed; spray drying the sol to obtain spherical precursor powder, calcining the precursor powder in an inert gas atmosphere for a certain time, and cooling the calcined precursor powder along with a furnace to obtain the lithium-rich oxide Li with the core-shell structure5FeO4and/C. Li prepared by the invention5FeO4the/C has no strict requirement on environment, can be coated with the anode material, has simple operation, does not need to modify the existing production line and process, greatly reduces the cost, and the prepared Li5FeO4The purity of the/C is high, and the existing Li is solved5FeO4The synthesis conditions are harsh and sensitive to the environment.

Description

Synthesis process of lithium-rich oxide and lithium ion battery containing lithium-rich oxide
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a synthesis process of a lithium-rich oxide and a lithium ion battery containing the lithium-rich oxide.
Background
The cathode of the current commercial lithium ion battery mainly adopts graphite materials, and the capacity matching of the anode material and the cathode material is one of key parameters in the design process of the lithium ion battery, and directly influences the cycle life of the lithium ion battery. The design capacity of the negative electrode material is usually 5-15% higher than that of the positive electrode material, because in the formation process, an SEI film of a lithiated compound is formed on the interface of the negative electrode, meanwhile, part of lithium inserted into the negative electrode can not be taken out to participate in normal charge-discharge cycle of the lithium ion battery, because the graphite of the negative electrode of the lithium ion battery does not contain lithium in the initial state, the source of the lithium is only the positive electrode material, about 7-10% of active lithium is lost due to the formation of the SEI film, and the loss of the lithium can cause the reduction of the battery capacity, the reduction of the coulombic efficiency and the deterioration of the cycle performance. With the continuous improvement of the energy density of the lithium ion battery, a new lithium source is introduced to carry out prelithiation on the battery, the first efficiency of the battery is improved, the cycle performance is improved, and the application of a lithium supplement process is particularly urgent.
Li5FeO4Is a lithium-rich metal oxide with an inverse fluorite structure, the theoretical specific capacity is up to 867mAh/g, and in addition, Li5FeO4Is low in the first charge-discharge efficiency, so Li5FeO4Is an ideal pre-intercalation additive and decomposes and provides lithium during the first charge but does not participate in the subsequent charge-discharge process. However, Li5FeO4Is very sensitive to water, and can produce lithium compound impurities when contacting a small amount of water in the air at normal temperature, so that the performance of the material is reduced, the polarization is increased, and high-purity Li is prepared5FeO4Particularly difficult. Therefore, how to increase Li5FeO4The purity of the product becomes a difficult point and a hot point for future research.
Disclosure of Invention
The invention aims to provide a synthesis process of a lithium-rich oxide and a lithium ion battery containing the lithium-rich oxide, wherein Li5FeO4The preparation process of the/C composite material is simple and controllable, the industrial production is easy to realize, and carbon decomposed by the organic carbon source is coated on Li5FeO4Surface of Li5FeO4the/C can effectively prevent water, can be coated with the anode material, is simple to operate, does not need to modify the existing production line and process, greatly reduces the cost, and the prepared Li5FeO4The purity of the/C is high, and the existing Li is solved5FeO4The synthesis conditions are harsh and sensitive to the environment.
Li containing in-situ coated core-shell structure prepared by the invention5FeO4The preparation process of the/C material can realize that carbon is firmly wrapped in Li after sintering5FeO4The surface of the lithium ion battery leads the prepared Li of the lithium ion battery to be repeatedly recycled for many times5FeO4Still in a wrapped state, can still realize the waterproof effect and solve the problemLi in the existing lithium ion battery5FeO4High hardness, difficult breakage, and generating lithium compound impurities after meeting water, which causes the problem that the performance of the material is reduced and the polarization is increased.
The lithium ion battery prepared by the invention has good cycle performance, and solves the problem that the battery can not be recycled for a long time due to the loss of lithium in the cycle process of the lithium ion battery prepared by the existing method.
The purpose of the invention can be realized by the following technical scheme:
a synthesis process of lithium-rich oxide comprises the following specific synthesis processes:
step 1: weighing a lithium source and an iron source with a proper molar ratio, dispersing the lithium source and the iron source in deionized water, and after the lithium source and the iron source are completely dissolved, weighing a proper amount of organic carbon source and adding the organic carbon source into the solution;
step 2: stirring the solution of step 1 at 80 ℃ until sol is formed;
and step 3: spray drying the sol obtained in the step 2 to obtain spherical precursor powder, calcining the precursor powder in an inert gas atmosphere for a certain time, and cooling with a furnace to obtain the lithium-rich oxide Li with the core-shell structure5FeO4/C。
Preferably, in the step 1, the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lithium lactate, lithium nitrate, lithium oxalate and lithium oxide.
Preferably, the iron source in step 1 is one or more of ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, and ferric citrate.
Preferably, the organic carbon source in step 1 is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polypyrrole, fatty alcohol-polyoxyethylene ether, sucrose, glucose, citric acid, ascorbic acid and polyoxyethylene fatty acid ester.
Preferably, in the step 1, the molar ratio of Li in the lithium source to Fe in the iron source is 5.0-6.5:1, and the mass ratio of the organic carbon source to the iron source is 0.5-2: 1.
Preferably, the air inlet temperature of the spray drying in the step 3 is 150-250 ℃, and the air outlet temperature is 80-150 ℃.
Preferably, the protective atmosphere in step 3 is one or more of nitrogen, argon, helium and neon.
Preferably, the calcination temperature in the step 3 is 600-1000 ℃, and the calcination time is 18-96 h.
A lithium ion battery containing the lithium-rich oxide is prepared by the following process:
the first step is to mix the positive electrode active material and Li5FeO4Adding the/C additive, the conductive agent and the binder into a solvent, uniformly mixing, and performing subsequent treatment to obtain a lithium ion battery positive pole piece;
the second step is that: adding a negative active material, a conductive agent, a dispersing agent and SBR into a solvent, uniformly mixing, and performing subsequent treatment to obtain a lithium ion battery negative pole piece;
the third step: then stacking the negative plate, the diaphragm and the positive plate in sequence, injecting electrolyte, and packaging to assemble the power soft package battery of 5 Ah;
the fourth step: and (4) carrying out formation treatment on the power soft package battery prepared in the third step, and then carrying out multiplying power and cycle life test on the power soft package battery.
Preferably, the positive electrode active material in the first step is one of nickel cobalt lithium manganate 523, nickel cobalt lithium 622, nickel cobalt lithium 811, lithium iron phosphate, lithium cobaltate, or lithium manganate.
Preferably, the conductive agent in the first step is acetylene black or ketjen black.
Preferably, the binder in the first step is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone, polypropylene, polyethylene, polyurethane, polyamide and polyamide-imide.
Preferably, the solvent in the first step is one or more of N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide, tetrahydrofuran and acetone.
Preferably, the mass ratio of the positive electrode active material, the lithium-rich oxide, the conductive agent and the binder in the first step is 94-85:1-15:3-4: 2-3.
Preferably, the negative active material in the first step is natural graphite or artificial graphite.
Preferably, the conductive agent in the second step is one or more of acetylene black, carbon black and graphite.
Preferably, the dispersing agent in the second step is one or more of carboxymethyl cellulose, carboxypropyl methyl cellulose, methyl cellulose or alkali metal salts thereof; the alkali metal is one of Na, K and Li.
Preferably, the mass ratio of the carbon powder, the conductive agent, the dispersing agent and the SBR in the second step is 95.8-94.5:1-1.5:1.2-1.5: 2.0-2.5.
Preferably, in the third step, the separator is a single body of polyethylene, polypropylene or a porous film made of polyolefin, a laminate, an extended film of the above resin mixture, or a fibrous nonwoven fabric made of at least one constituent material selected from the group consisting of cellulose, polyester and polypropylene.
Preferably, the electrolyte in the third step is a normal commercial lithium ion battery electrolyte without special requirements.
Preferably, the formation treatment process in the fourth step is charging to 3.5-3.85V by 0.2C current, and stabilizing treatment is carried out for 12-24 h.
Preferably, the cycle life test in the fourth step is that the first charging is carried out by constant current or constant voltage charging at 0.2-0.5C, the cut-off voltage is 3.95-4.2V, the first discharging is carried out by constant current discharging at 1-5C, the cut-off voltage is 2.0-2.5V, the second charging is carried out by constant current or constant voltage charging at 1-5C, the cut-off voltage is 3.65-4.2V, and the second discharging is carried out by constant current discharging at 1-5C, the cut-off voltage is 2.0-2.5V. And small current is adopted during first charging, so that lithium in the material can be completely extracted.
The invention has the beneficial effects that:
1. li with in-situ coated core-shell structure prepared by the invention5FeO4a/C positive electrode material in which Li is coated with carbon decomposed from an organic carbon source5FeO4Surface, barrier to Li5FeO4The surface is directly contacted with the air, which can effectively prevent water,eliminating or mitigating the formation of impurity phases on the surface of the material, Li5FeO4The preparation process of the/C composite material is simple and controllable, the industrial production is easy to realize, and the problem of Li in the prior art is solved5FeO4The method has the problem that the conditions are harsh in the air, and industrial production cannot be realized.
2. Li containing in-situ coated core-shell structure prepared by the invention5FeO4The preparation process of the/C material can realize that carbon is firmly wrapped in Li after sintering5FeO4The surface of the lithium ion battery enables the Li5FeO4 to be still in a wrapped state after repeated and cyclic use for many times, the waterproof effect can be still realized, and the problems that the Li5FeO4 in the existing lithium ion battery is high in hardness and not easy to break, and lithium compound impurities are generated after the lithium ion battery meets water, so that the performance of the material is reduced, and the polarization is increased are solved.
3. Li prepared by the invention5FeO4the/C has no harsh requirement on the environment, can be coated with the anode material, is simple to operate, does not need to modify the existing production line and process, and greatly reduces the cost.
4. Li of the invention when the battery is charged for the first time5FeO4The released partial or all lithium ions reduce the first irreversible (SEI film formation) of the battery and the loss of lithium in the circulation process, the first efficiency and the energy density of the lithium ion battery are obviously improved, the activity of the product after the lithium ions are released is extremely low, the product cannot be embedded with lithium or dissolved again, and the product is coated on the Li5FeO4The carbon layer on the surface can increase the electronic conductivity of the electrode, the cycling stability of the battery is obviously improved by the coordination effect between the carbon layer and the electrode, and the problem of poor cycling performance of the conventional lithium ion battery is solved.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 shows Li in example 1 of the present invention5FeO4A scanning electron micrograph of/C;
FIG. 2 is a graph showing cycle life at 1C for composite electrodes of examples 1 to 4 of the present invention and comparative example 1.
Detailed Description
Example 1:
as shown in figure 1, lithium hydroxide and ferric nitrate are weighed according to a molar ratio of 5.5:1, dissolved in deionized water, polyethylene glycol-4000 is weighed according to a mass ratio of 2:1 of polyethylene glycol-4000 to ferric nitrate, added into the solution, stirred at 80 ℃ to form sol, the sol is subjected to spray drying (the air inlet temperature is 200 ℃, the air outlet temperature is 100 ℃) to obtain spherical precursor powder, the obtained precursor powder is calcined at 800 ℃ in an argon atmosphere for 24 hours, and furnace cooling is carried out to obtain Li with a core-shell structure5FeO4/C。
Using nickel cobalt lithium manganate 811 and Li5FeO4and/C is a positive electrode active substance, and is weighed according to the mass ratio of 90:5:3:2 to acetylene black and polyvinylidene fluoride. Then polyvinylidene fluoride (PVDF) is added into N-methyl pyrrolidone for dispersion, and acetylene black, nickel cobalt lithium manganate 811 and Li are sequentially added after complete dispersion5FeO4C, uniformly stirring, and obtaining the positive plate through size mixing, coating, drying and rolling;
weighing graphite powder, SPC65, CMC and SBR according to a mass ratio of 95:1.5:1.5:2, adding the graphite powder, the SPC65, the CMC and the SBR into deionized water, stirring the mixture evenly, and obtaining a negative plate through size mixing, coating, drying and rolling;
welding the manufactured positive and negative pole pieces with tabs, transferring to an assembly process, assembling the positive and negative pole pieces with an isolating film into a core liquid injection of a laminated structure, and packaging into a 5Ah soft package battery; the test pieces were charged to 3.95V at 0.2C, and after standing for 12 hours, the test pieces were subjected to 1C, 2C, 5C rate and 2C cycle performance tests.
Example 2
Weighing lithium nitrate and ferric chloride according to a molar ratio of 6:1, dissolving in deionized water, weighing polyacrylic acid according to a mass ratio of 1.5:1 of polyacrylic acid to ferric chloride, adding the polyacrylic acid into the solution, stirring at 80 ℃ to form sol, performing spray drying on the sol (the air inlet temperature is 180 ℃, the air outlet temperature is 90 ℃) to obtain spherical precursor powder, calcining the precursor powder in a nitrogen atmosphere at 900 ℃ for 48 hours, and cooling with a furnace to obtain the Li with the core-shell structure5FeO4/C。
With nickel cobalt manganic acidLithium 622 and Li5FeO4and/C is positive electrode active substance, and is weighed according to the mass ratio of 91:4:3:2 with acetylene black and polyvinylidene fluoride. Then polyvinylidene fluoride (PVDF) is added into N-methyl pyrrolidone for dispersion, and acetylene black, nickel cobalt lithium manganate 622 and Li are sequentially added after complete dispersion5FeO4C, uniformly stirring, and obtaining the positive plate through size mixing, coating, drying and rolling;
the fabrication of the negative electrode sheet, the cell assembly, the formation and the electrochemical performance test were the same as those of example 1.
Example 3
Weighing lithium oxalate and ferrous chloride according to a molar ratio of 5.8:1, dissolving the lithium oxalate and the ferrous chloride in deionized water, weighing polyoxyethylene fatty acid ester according to a mass ratio of 1:1 of the polyoxyethylene fatty acid ester and the ferrous chloride, adding the polyoxyethylene fatty acid ester into the solution, stirring the mixture at 80 ℃ to form sol, performing spray drying on the sol (the air inlet temperature is 250 ℃ and the air outlet temperature is 150 ℃) to obtain spherical precursor powder, calcining the precursor powder for 64 hours at 850 ℃ in a nitrogen atmosphere, and cooling the precursor powder along with a furnace to obtain the Li with the core-shell structure5FeO4/C。
Taking the nickel cobalt lithium manganate 523 and the Li5FeO4/C as positive active substances, weighing the positive active substances, acetylene black and polyvinylidene fluoride according to the mass ratio of 87:8:3:2, then adding the polyvinylidene fluoride (PVDF) into N-methyl pyrrolidone for dispersion, and sequentially adding the acetylene black, the nickel cobalt lithium manganate 523 and the Li after complete dispersion5FeO4C, uniformly stirring, and obtaining the positive plate through size mixing, coating, drying and rolling;
the fabrication of the negative electrode sheet, the cell assembly, the formation and the electrochemical performance test were the same as those of example 1.
Example 4
Weighing lithium metaborate and ferrous nitrate according to a molar ratio of 6:1, dissolving the lithium metaborate and the ferrous nitrate into deionized water, weighing polyethylene glycol-6000 according to a mass ratio of 0.5:1 of polyethylene glycol-6000 to the ferrous nitrate, adding the polyethylene glycol-6000 to the solution, stirring the solution at 80 ℃ to form sol, performing spray drying on the sol (the air inlet temperature is 230 ℃, the air outlet temperature is 110 ℃) to obtain spherical precursor powder, calcining the precursor powder for 96 hours at 600 ℃ in a nitrogen atmosphere, and cooling the precursor powder along with a furnace to obtain the Li with the core-shell structure5FeO4/C；
Mixing LiFePO4And Li5FeO4and/C is a positive electrode active substance, and is weighed according to the mass ratio of 89:5:3:3 with acetylene black and polyvinylidene fluoride. Then polyvinylidene fluoride (PVDF) is added into N-methyl pyrrolidone for dispersion, and acetylene black and LiFePO are sequentially added after complete dispersion4And Li5FeO4C, uniformly stirring, and obtaining the positive plate through size mixing, coating, drying and rolling;
the fabrication of the negative electrode sheet, the cell assembly, the formation and the electrochemical performance test were the same as those of example 1.
Comparative example 1
The same as in example 1 except that nickel cobalt lithium manganate 811 was used as a positive electrode active material and was weighed in a mass ratio of acetylene black to polyvinylidene fluoride of 95:3:2, and as can be seen from fig. 2, nickel cobalt lithium manganate 811 directly used as a positive electrode active material contained Li in comparison with Li5FeO4The positive electrode active material/C has a low capacity retention rate as a whole.
The rate capability of inventive examples 1-4 and comparative example 1 are shown in table 1.
TABLE 1 Rate Performance of examples 1-4 and comparative example 1
Figure BDA0001719659750000081
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. The synthesis process of the lithium-rich oxide is characterized by comprising the following specific synthesis processes:
step 1: weighing a lithium source and an iron source with a proper molar ratio, dispersing the lithium source and the iron source in deionized water, and after the lithium source and the iron source are completely dissolved, weighing a proper amount of organic carbon source and adding the organic carbon source into the solution;
step 2: stirring the solution of step 1 at 80 ℃ until sol is formed;
and step 3: spray drying the sol obtained in the step 2 to obtain spherical precursor powder, calcining the precursor powder in an inert gas atmosphere for a certain time, and cooling with a furnace to obtain the lithium-rich oxide Li with the core-shell structure5FeO4/C。
2. The process for synthesizing lithium-rich oxide according to claim 1, wherein the lithium source in step 1 is one or more selected from lithium hydroxide, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lithium lactate, lithium nitrate, lithium oxalate and lithium oxide; the iron source is one or more of ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate and ferric citrate; the organic carbon source is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polypyrrole, fatty alcohol-polyoxyethylene ether, sucrose, glucose, citric acid, ascorbic acid and polyoxyethylene fatty acid ester.
3. The process for synthesizing lithium-rich oxide according to claim 1, wherein the molar ratio of Li in the lithium source to Fe in the iron source in step 1 is 5.0-6.5:1, and the mass ratio of the organic carbon source to the iron source is 0.5-2: 1.
4. The process for synthesizing lithium-rich oxide according to claim 1, wherein the air inlet temperature of the spray drying in the step 3 is 150-250 ℃, and the air outlet temperature is 80-150 ℃; the inert gas is one or more of argon, helium and neon; the calcination temperature is 600-1000 ℃, and the calcination time is 18-96 h.
5. The process for synthesizing lithium-rich oxide according to claim 1, wherein the synthesized lithium-rich oxide is applied to a lithium ion battery, and the lithium ion battery is prepared by the following process:
the first step is to mix the positive electrode active material and Li5FeO4Adding the/C additive, the conductive agent and the binder into a solvent, uniformly mixing, and performing subsequent treatment to obtain a lithium ion battery positive pole piece;
the second step is that: adding a negative active material, a conductive agent, a dispersing agent and SBR into a solvent, uniformly mixing, and performing subsequent treatment to obtain a lithium ion battery negative pole piece;
the third step: then stacking the negative pole piece, the diaphragm and the positive pole piece in sequence, injecting electrolyte and packaging to assemble the power soft package battery of 5 Ah;
the fourth step: and (4) carrying out formation treatment on the power soft package battery prepared in the third step, and then carrying out multiplying power and cycle life test on the power soft package battery.
6. The process for synthesizing a lithium-rich oxide according to claim 5, wherein the positive active material in the first step is one of lithium nickel cobalt manganese 523, 622, 811, lithium iron phosphate, lithium cobaltate, or lithium manganese; the conductive agent is acetylene black or Ketjen black; the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone, polypropylene, polyethylene, polyurethane, polyamide and polyamide-imide; the solvent is one or more of N-methylpyrrolidone, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide, tetrahydrofuran and acetone.
7. The process for synthesizing a lithium-rich oxide according to claim 5, wherein the first step is a process in which the positive electrode active material, Li5FeO4The mass ratio of the conductive agent to the binder is 94-85:1-15:3-4: 2-3.
8. The process for synthesizing lithium-rich oxide according to claim 5, wherein the negative active material in the second step is natural graphite or artificial graphite; the conductive agent is one or more of carbon black and graphite; the dispersant is one or more of carboxymethyl cellulose, carboxypropyl methyl cellulose, methyl cellulose or alkali metal salts thereof; the alkali metal is one of Na, K and Li; and the mass ratio of the negative active material, the conductive agent, the dispersing agent and the SBR is 95.8-94.5:1-1.5:1.2-1.5: 2.0-2.5.
9. The process for synthesizing a lithium-rich oxide according to claim 5, wherein the separator in the third step is a single-layer body or a laminated body of a porous thin film made of polyolefin or a fibrous nonwoven fabric made of at least one member selected from the group consisting of cellulose, polyester and polypropylene.
10. The process for synthesizing lithium-rich oxide according to claim 5, wherein the fourth step of the chemical conversion treatment process comprises charging to 3.5-3.85V at 0.2C current, and performing voltage stabilization treatment for 12-24 h; the cycle life test process comprises the steps of carrying out constant current charging at 0.2-0.5C for the first time, wherein the cut-off voltage is 3.95-4.2V, carrying out constant current discharging at 1-5C for the first time, the cut-off voltage is 2.0-2.5V, carrying out constant current charging at 1-5C for the second time, the cut-off voltage is 3.65-4.2V, and carrying out constant current discharging at 1-5C for the second time, wherein the cut-off voltage is 2.0-2.5V.
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