CN108878849A - The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium - Google Patents

The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium Download PDF

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CN108878849A
CN108878849A CN201810725733.XA CN201810725733A CN108878849A CN 108878849 A CN108878849 A CN 108878849A CN 201810725733 A CN201810725733 A CN 201810725733A CN 108878849 A CN108878849 A CN 108878849A
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lithium
oxidate
ion battery
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CN108878849B (en
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陈伟
王海文
范进雷
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Jiangxi Huaxin Rui Automobile Energy Technology Co Ltd
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Jiangxi Huaxin Rui Automobile 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

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  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention discloses a kind of synthesis technologies of rich oxidate for lithium containing the lithium ion battery of rich oxidate for lithium, wherein the specific synthesis process of rich oxidate for lithium is as follows：Lithium source, the source of iron for weighing appropriate molar ratio, disperse them in deionized water, weigh suitable organic carbon source until completely dissolved and are added in above-mentioned solution；Solution is stirred at 80 DEG C until forming colloidal sol；Aerosol spray is dried to obtain spherical precursor powder, then calcines precursor powder certain time under atmosphere of inert gases, furnace cooling obtains the rich oxidate for lithium Li of core-shell structure5FeO4/C.Li prepared by the present invention5FeO4/ C is not harsh to environmental requirement, can be coated with together with positive electrode, easy to operate, does not need to be transformed existing producing line and technique, greatly reduces cost, and the Li prepared5FeO4/ C purity is high, solves existing Li5FeO4Synthesis condition is harsh, and environmentally sensitive problem.

Description

The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium
Technical field
The invention belongs to field of lithium ion battery, it is related to a kind of synthesis technology of rich oxidate for lithium and containing the richness oxidate for lithium Lithium ion battery.
Background technique
Current commercialized negative electrode of lithium ion battery mainly uses graphite type material, the capacity of positive electrode, negative electrode material Matching is one of the key parameter in lithium ion battery design process, directly affects the cycle life of lithium ion battery.It is usually negative The design capacity of pole material is 5-15% higher than the design capacity of positive electrode, this is because during chemical conversion, cathode interface It will form the SEI film of lithiumation object, while the lithium for being partially submerged into cathode cannot deviate to participate in the normal charge and discharge of lithium ion battery again Circulation, since negative electrode of lithium ion battery graphite is free from lithium in the initial state, the source of lithium is only positive material Material, since the active lithium of about 7-10% can be lost in the formation of SEI film, the loss of lithium will lead to battery capacity reduction, coulombic efficiency It reduces, cycle performance is deteriorated.With the continuous improvement of lithium ion battery energy density, introduces new lithium source and pre- lithium is carried out to battery Change, improve the first charge discharge efficiency of battery, improve cycle performance, the application for mending lithium technique just seems especially urgent.
Li5FeO4It is a kind of rich lithium metal oxide of antifluorite structure, theoretical specific capacity is up to 867mAh/g, in addition Li5FeO4First charge-discharge efficiency it is low, therefore Li5FeO4It is a kind of ideal pre- embedding lithium additive, and in the initial charge phase Between decompose and lithium be provided but is not involved in subsequent charge and discharge process.But Li5FeO4It is very sensitive to water, it is contacted under room temperature empty A small amount of water will produce lithium compound impurity in gas, cause the performance of material to decline polarization and become larger, prepare high-purity Li5FeO4It is particularly difficult.Therefore, how Li is improved5FeO4Purity become the difficult point studied from now on and hot spot.
Summary of the invention
The purpose of the present invention is to provide a kind of synthesis technology of rich oxidate for lithium and the lithium ion containing the richness oxidate for lithium Battery, Li5FeO4/ C composite preparation process is simple, controllable and be easily industrialized production, is decomposed by organic carbon source Carbon coating in Li5FeO4Surface, so that Li5FeO4/ C can effective waterproof, can be coated with together with positive electrode, operate Simply, it does not need to be transformed existing producing line and technique, greatly reduces cost, and the Li prepared5FeO4/ C purity Height solves existing Li5FeO4Synthesis condition is harsh, and environmentally sensitive problem.
Li prepared by the present invention containing in-stiu coating core-shell structure5FeO4/ C-material, in preparation process after oversintering energy Enough realize that carbon is firmly wrapped in Li5FeO4Surface so that preparation lithium ion battery through multiplicating be recycled after Li5FeO4Still in package status, it still is able to realize the effect of waterproof, and solve in existing lithium ion battery Li5FeO4Hardness is high, non-breakable, and generates lithium compound impurity after meeting water, and the performance of material is caused to decline what polarization became larger Problem.
Cycle performance of lithium ion battery prepared by the present invention is good, and the lithium ion battery for solving existing method preparation is recycling The loss of lithium in the process, the problem of causing battery that cannot be recycled for a long time.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of synthesis technology of richness oxidate for lithium, specific synthesis process are as follows：
Step 1：Lithium source, the source of iron for weighing appropriate molar ratio, disperse them in deionized water, claim until completely dissolved Suitable organic carbon source is taken to be added in above-mentioned solution；
Step 2：The solution of step 1 is stirred at 80 DEG C until forming colloidal sol；
Step 3：Step 2 gained aerosol spray is dried to obtain spherical precursor powder, then by precursor powder lazy It is calcined certain time under property atmosphere, furnace cooling obtains the rich oxidate for lithium Li of core-shell structure5FeO4/C。
Preferably, lithium source is lithium hydroxide, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lactic acid in the step 1 One or more of lithium, lithium nitrate, lithium oxalate, lithia.
Preferably, source of iron is ferric nitrate, ferrous nitrate, iron chloride, frerrous chloride, ferric sulfate, sulfuric acid Asia in the step 1 One or more of iron, ironic citrate.
Preferably, organic carbon source is polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polypyrrole, fatty alcohol in the step 1 One or more of polyoxyethylene ether, sucrose, glucose, citric acid, ascorbic acid and polyoxyethylene fatty acid ester.
Preferably, the molar ratio of the Fe in the Li and source of iron in the step 1 in lithium source is 5.0-6.5:1, organic carbon source It is 0.5-2 with source of iron mass ratio:1.
Preferably, the inlet air temperature being spray-dried in the step 3 is 150-250 DEG C, and leaving air temp is 80-150 DEG C.
Preferably, protective atmosphere is one or more of nitrogen, argon gas, helium, neon in the step 3.
Preferably, calcination temperature is 600-1000 DEG C in the step 3, calcination time 18-96h.
A kind of lithium ion battery containing the richness oxidate for lithium, the preparation process of the lithium ion battery are as follows：
The first step:By positive electrode active materials, Li5FeO4/ C additive, conductive agent and binder are added in solvent and mix It is even to obtain anode slice of lithium ion battery through subsequent processing；
Second step：Negative electrode active material, conductive agent, dispersing agent and SBR are added in solvent and are uniformly mixed through subsequent place Reason obtains lithium ion battery negative electrode；
Third step：Negative electrode tab, diaphragm, positive plate are stacked in order again, are assembled into the dynamic of 5Ah after injection electrolyte encapsulation Power soft-package battery；
4th step：After the power soft-package battery prepared in third step is carried out chemical conversion treatment, multiplying power and circulation are carried out to it Life test.
Preferably, positive electrode active materials are nickle cobalt lithium manganate 523, nickle cobalt lithium manganate 622, nickel cobalt mangaic acid in the first step One of lithium 811, LiFePO4, cobalt acid lithium or LiMn2O4.
Preferably, conductive agent is acetylene black or Ketjen black in the first step.
Preferably, binder is Kynoar, polytetrafluoroethylene (PTFE), polyvinylpyrrolidone, poly- third in the first step The one or more of alkene, polyethylene, polyurethane, polyamide, polyamidoimide.
Preferably, solvent is N-Methyl pyrrolidone, n,N-Dimethylformamide, N, N- diethyl first in the first step One or more of amide, dimethyl sulfoxide, tetrahydrofuran, acetone.
Preferably, positive active material in the first step, rich oxidate for lithium, conductive agent, binder mass ratio be 94- 85:1-15:3-4:2-3。
Preferably, negative electrode active material is natural graphite, artificial graphite in the first step.
Preferably, conductive agent is one or more of acetylene black, carbon black, graphite in the second step.
Preferably, in the second step dispersing agent be carboxymethyl cellulose, carboxylic propyl methocel, methylcellulose or One or more of their alkali metal salt；Alkali metal is one of Na, K, Li.
Preferably, carbon powder in the second step, conductive agent, dispersing agent, SBR mass ratio be 95.8-94.5:1-1.5: 1.2-1.5:2.0-2.5。
Preferably, the third step septation is polyethylene, polypropylene or the porous membrane being made of polyolefin Single adult, laminated body and above-mentioned resin compound stretched PTFE film or be by cellulose, polyester and polypropylene extremely The fabric nonwoven cloth that a kind of few constituent material is constituted.
Preferably, electrolyte without particular/special requirement is normal commercialized lithium-ion battery electrolytes in the third step.
Preferably, chemical conversion treatment process is to charge to 3.5-3.85V with 0.2C electric current in the 4th step, steady pressure treatment 12-24h。
Preferably, cycle life test charges for first time and carries out constant current or constant pressure using 0.2-0.5C in the 4th step Charging, blanking voltage 3.95-4.2V are discharged for the first time using 1-5C progress constant-current discharge, blanking voltage 2.0-2.5V, the Recharging carries out constant current or constant-voltage charge, blanking voltage 3.65-4.2V using 1-5C, and second of electric discharge is carried out using 1-5C Constant-current discharge, blanking voltage 2.0-2.5V.Low current is used when initial charge, and the lithium in material can be made completely out.
Beneficial effects of the present invention：
1, the Li of in-stiu coating core-shell structure prepared by the present invention5FeO4/ C positive electrode material, the carbon decomposed by organic carbon source It is coated on Li5FeO4Surface obstructs Li5FeO4Surface is directly contacted with air, can effective waterproof, elimination or alleviation material The generation of surface impurity phase, Li5FeO4/ C composite preparation process is simple, controllable and be easily industrialized production, solution Li in the prior art5FeO4The problem of existence condition is harsh in air, cannot achieve industrial production.
2, the Li prepared by the present invention containing in-stiu coating core-shell structure5FeO4/ C-material, in preparation process after oversintering It can be realized carbon and be firmly wrapped in Li5FeO4Surface so that preparation lithium ion battery through multiplicating be recycled after Li5FeO4 still is able to realize the effect of waterproof still in package status, and solves in existing lithium ion battery Li5FeO4 hardness is high, non-breakable, and generates lithium compound impurity after meeting water, causes the performance of material to decline polarization and becomes larger The problem of.
3, Li prepared by the present invention5FeO4/ C is not harsh to environmental requirement, can be coated with together with positive electrode, operation letter It is single, it does not need to be transformed existing producing line and technique, greatly reduces cost.
4, present invention Li in battery initial charge5FeO4Some or all of release lithium ion reduces battery and for the first time can not The loss of lithium, significantly improves the first charge discharge efficiency and energy density of lithium ion battery in inverse (forming SEI film) and cyclic process, and Lytic activity after discharging lithium ion is extremely low, will not embedding lithium or dissolution again, and be coated on Li5FeO4The carbon-coating on surface can To increase the electronic conductivity of electrode, coordinating effect between the two makes the cyclical stability of battery be significantly improved, and solves The problem of existing cycle performance of lithium ion battery difference.
Detailed description of the invention
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
Fig. 1 is Li in the embodiment of the present invention 15FeO4The scanning electron microscope (SEM) photograph of/C；
Fig. 2 is the cycle life curve figure of 1-4 of the embodiment of the present invention and 1 combination electrode of comparative example at 1C.
Specific embodiment
Embodiment 1：
As shown in Figure 1, being in molar ratio 5.5:1 weighs lithium hydroxide and ferric nitrate, is dissolved in deionized water, by poly- second two Alcohol -4000 and ferric nitrate mass ratio are 2:1, which weighs polyethylene glycol-4000, is added in above-mentioned solution, and 80 DEG C of stirrings form colloidal sol, Gained colloidal sol is spray-dried (inlet air temperature is 200 DEG C, 100 DEG C of leaving air temp) and obtains spherical precursor powder, by institute Precursor powder calcined for 24 hours at 800 DEG C in argon atmosphere, furnace cooling up to core-shell structure Li5FeO4/C。
With nickle cobalt lithium manganate 811 and Li5FeO4/ C is positive active material, in mass ratio with acetylene black, Kynoar It is 90:5:3:2 weigh.Then Kynoar (PVDF) is added in N-Methyl pyrrolidone and is dispersed, dispersion is complete After sequentially add acetylene black, nickle cobalt lithium manganate 811 and Li5FeO4/ C, stirs evenly, and by sizing mixing, being coated with, dry, roll-in obtains Positive plate；
It is in mass ratio 95 by graphite powder and SPC65, CMC, SBR:1.5:1.5:2 weigh, and are add to deionized water, stir It mixes uniformly, by sizing mixing, being coated with, dry, roll-in obtains negative electrode tab；
Assembly process will be gone to after the positive/negative plate soldering polar ear made, lamination is assembled into together with isolation film Core fluid injection and the soft-package battery for being encapsulated as 5Ah；3.95V is charged to 0.2C, after static 12 hours, 1C, 2C, 5C are carried out to it Multiplying power and the test of 2C cycle performance.
Embodiment 2
It is in molar ratio 6:1 weighs lithium nitrate and iron chloride, is dissolved in deionized water, by polyacrylic acid and chlorination weight of iron Than being 1.5:1, which weighs polyacrylic acid, is added in above-mentioned solution, and 80 DEG C of stirrings form colloidal sol, and gained colloidal sol is spray-dried (inlet air temperature is 180 DEG C, 90 DEG C of leaving air temp) obtains spherical precursor powder, by gained precursor powder in nitrogen atmosphere Calcine 48h at 900 DEG C, furnace cooling up to core-shell structure Li5FeO4/C。
With nickle cobalt lithium manganate 622 and Li5FeO4/ C is positive active material, is in mass ratio with acetylene black, Kynoar 91:4:3:2 weigh.Then Kynoar (PVDF) is added in N-Methyl pyrrolidone and is dispersed, after dispersion completely Sequentially add acetylene black, nickle cobalt lithium manganate 622 and Li5FeO4/ C, stirs evenly, and by sizing mixing, being coated with, dry, roll-in obtains just Pole piece；
The production of negative electrode tab, battery assembly, chemical conversion and electrochemical property test are same as Example 1.
Embodiment 3
It is in molar ratio 5.8:1 weighs lithium oxalate and frerrous chloride, is dissolved in deionized water, by polyoxyethylene fatty acid ester It is 1 with frerrous chloride mass ratio:1, which weighs polyoxyethylene fatty acid ester, is added in above-mentioned solution, and 80 DEG C of stirrings form colloidal sol, will Gained colloidal sol is spray-dried (inlet air temperature is 250 DEG C, 150 DEG C of leaving air temp) and obtains spherical precursor powder, by gained Precursor powder calcines 64h in nitrogen atmosphere at 850 DEG C, furnace cooling up to core-shell structure Li5FeO4/C。
Using nickle cobalt lithium manganate 523 and Li5FeO4/C as positive active material, in mass ratio with acetylene black, Kynoar It is 87:8:3:2 weigh, and then Kynoar (PVDF) is added in N-Methyl pyrrolidone and is dispersed, and dispersion is complete After sequentially add acetylene black, nickle cobalt lithium manganate 523 and Li5FeO4/ C, stirs evenly, and by sizing mixing, being coated with, dry, roll-in obtains Positive plate；
The production of negative electrode tab, battery assembly, chemical conversion and electrochemical property test are same as Example 1.
Embodiment 4
It is in molar ratio 6:1 weighs lithium metaborate and ferrous nitrate, is dissolved in deionized water, by polyethylene glycol-6000 with Ferrous nitrate mass ratio is 0.5:1, which weighs polyethylene glycol-6000, is added in above-mentioned solution, and 80 DEG C of stirrings form colloidal sol, by institute Colloidal sol is spray-dried (inlet air temperature be 230 DEG C, 110 DEG C of leaving air temp) and obtains spherical precursor powder, before gained Drive body powder and calcine 96h at 600 DEG C in nitrogen atmosphere, furnace cooling up to core-shell structure Li5FeO4/C；
By LiFePO4And Li5FeO4/ C is positive active material, is in mass ratio 89 with acetylene black, Kynoar:5: 3:3 weigh.Then Kynoar (PVDF) is added in N-Methyl pyrrolidone and is dispersed, successively added after dispersion completely Enter acetylene black, LiFePO4And Li5FeO4/ C, stirs evenly, and by sizing mixing, being coated with, dry, roll-in obtains positive plate；
The production of negative electrode tab, battery assembly, chemical conversion and electrochemical property test are same as Example 1.
Comparative example 1
It is in mass ratio 95 with acetylene black, Kynoar in addition to being positive active material by nickle cobalt lithium manganate 811:3:2 It weighs, it is directly positive active material with nickle cobalt lithium manganate 811 as shown in Figure 2 that remaining is same as Example 1, compared to containing Li5FeO4The positive active material of/C, capacity retention rate are integrally lower.
1-4 of the embodiment of the present invention and the high rate performance of comparative example 1 are as shown in table 1.
1 embodiment 1-4 of table and 1 high rate performance of comparative example
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification, It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only It is limited by claims and its full scope and equivalent.

Claims (10)

1. the synthesis technology of rich oxidate for lithium, which is characterized in that specific synthesis process is as follows：
Step 1：Lithium source, the source of iron for weighing appropriate molar ratio, disperse them in deionized water, weigh until completely dissolved suitable The organic carbon source of amount is added in above-mentioned solution；
Step 2：The solution of step 1 is stirred at 80 DEG C until forming colloidal sol；
Step 3：Step 2 gained aerosol spray is dried to obtain spherical precursor powder, then by precursor powder in indifferent gas It is calcined certain time under body atmosphere, furnace cooling obtains the rich oxidate for lithium Li of core-shell structure5FeO4/C。
2. the synthesis of richness oxidate for lithium according to claim 1, which is characterized in that lithium source is hydroxide in the step 1 One or more of lithium, lithium carbonate, lithium acetate, lithium borate, lithium metaborate, lithium lactate, lithium nitrate, lithium oxalate, lithia；Iron Source is one or more of ferric nitrate, ferrous nitrate, iron chloride, frerrous chloride, ferric sulfate, ferrous sulfate, ironic citrate；Have Machine carbon source is polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polypyrrole, fatty alcohol polyoxyethylene ether, sucrose, glucose, lemon One or more of acid, ascorbic acid and polyoxyethylene fatty acid ester.
3. the synthesis of richness oxidate for lithium according to claim 1, which is characterized in that Li in the step 1 in lithium source and The molar ratio of Fe in source of iron is 5.0-6.5:1, organic carbon source and source of iron mass ratio are 0.5-2:1.
4. it is according to claim 1 richness oxidate for lithium synthesis, which is characterized in that be spray-dried in the step 3 into Air temperature is 150-250 DEG C, and leaving air temp is 80-150 DEG C；Protective atmosphere is one of nitrogen, argon gas, helium, neon Or it is several；Calcination temperature is 600-1000 DEG C, calcination time 18-96h.
5. the lithium ion battery according to claim 1 containing the richness oxidate for lithium, which is characterized in that the lithium ion battery is logical Cross following technical process preparation：
The first step:By positive electrode active materials, Li5FeO4/ C additive, conductive agent and binder, which are added in solvent, is uniformly mixed warp Subsequent processing obtains anode slice of lithium ion battery；
Second step：Negative electrode active material, conductive agent, dispersing agent and SBR are added to be uniformly mixed in solvent and obtained through subsequent processing To lithium ion battery negative electrode；
Third step：Negative electrode tab, diaphragm, positive plate are stacked in order again, the power that 5Ah is assembled into after injection electrolyte encapsulation is soft Packet battery；
4th step：After the power soft-package battery prepared in third step is carried out chemical conversion treatment, multiplying power and cycle life are carried out to it Test.
6. the lithium ion battery preparation process according to claim 5 containing rich oxidate for lithium, which is characterized in that described first In step positive electrode active materials be nickle cobalt lithium manganate 523, nickle cobalt lithium manganate 622, nickle cobalt lithium manganate 811, LiFePO4, cobalt acid lithium or One of LiMn2O4；Conductive agent is acetylene black or Ketjen black；Binder is Kynoar, polytetrafluoroethylene (PTFE), polyethylene pyrrole The one or more of pyrrolidone, polypropylene, polyethylene, polyurethane, polyamide, polyamidoimide；Solvent is N- methylpyrrole Alkanone, N,N-dimethylformamide, N, one of N- diethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone or several Kind.
7. the lithium ion battery preparation process according to claim 5 containing rich oxidate for lithium, which is characterized in that described first Positive active material in step, rich oxidate for lithium, conductive agent, binder mass ratio be 94-85:1-15:3-4:2-3.
8. the lithium ion battery preparation process according to claim 5 containing rich oxidate for lithium, which is characterized in that described second Negative electrode active material is natural graphite, artificial graphite in step；Conductive agent is one or more of acetylene black, carbon black, graphite；Point Powder is one or more of carboxymethyl cellulose, carboxylic propyl methocel, methylcellulose or their alkali metal salt； Alkali metal is one of Na, K, Li；And the mass ratio of carbon powder, conductive agent, dispersing agent, SBR are 95.8-94.5:1- 1.5:1.2-1.5:2.0-2.5。
9. the lithium ion battery preparation process according to claim 5 containing rich oxidate for lithium, which is characterized in that the third Step septation is single adult, laminated body and the above-mentioned tree of polyethylene, polypropylene or the porous membrane being made of polyolefin Fiber of the stretched PTFE film of lipoprotein mixture either by being constituted selected from least one of cellulose, polyester and polypropylene constituent material Non-woven fabrics.
10. the lithium ion battery preparation process according to claim 5 containing rich oxidate for lithium, which is characterized in that described Chemical conversion treatment process is to charge to 3.5-3.85V, steady pressure treatment 12-24h with 0.2C electric current in four steps；Cycle life test process Constant current or constant-voltage charge are carried out using 0.2-0.5C for first time charging, blanking voltage 3.95-4.2V, electric discharge uses for the first time 1-5C carries out constant-current discharge, blanking voltage 2.0-2.5V, and second of charging carries out constant current or constant-voltage charge, cut-off using 1-5C Voltage is 3.65-4.2V, and second of electric discharge carries out constant-current discharge, blanking voltage 2.0-2.5V using 1-5C.
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CN109817913A (en) * 2019-01-16 2019-05-28 江西中汽瑞华新能源科技有限公司 A kind of anode material for compound lithium ion battery and preparation method thereof
CN110048120A (en) * 2019-04-23 2019-07-23 王柯娜 A kind of preparation method of nanometer of ferrous acid lithium
CN110294494A (en) * 2019-07-25 2019-10-01 哈尔滨工业大学 Lithium vanadate anode mends lithium additive and its application
CN110459748A (en) * 2019-08-20 2019-11-15 湖北融通高科先进材料有限公司 A kind of carbon coating ferrous acid lithium material and preparation method thereof
CN110518223A (en) * 2019-09-06 2019-11-29 湖北融通高科先进材料有限公司 A kind of coating aluminium foil and preparation method thereof
CN111769288A (en) * 2020-08-13 2020-10-13 哈尔滨工业大学 Method for in-situ lithium supplement of lithium ion battery anode material
CN112054166A (en) * 2019-06-06 2020-12-08 苏州第一元素纳米技术有限公司 Core-shell structure electrochemical active material, preparation method and battery
CN112117433A (en) * 2020-09-01 2020-12-22 深圳市德方纳米科技股份有限公司 Preparation method of lithium ferrite
CN112117136A (en) * 2020-09-14 2020-12-22 东北石油大学 GO-CS coated potassium ferrate material and preparation method and application thereof
CN112164796A (en) * 2020-09-16 2021-01-01 合肥国轩高科动力能源有限公司 Pre-lithiation additive for positive electrode material of lithium ion battery and preparation method and application thereof
CN112490415A (en) * 2019-09-12 2021-03-12 湖南杉杉能源科技股份有限公司 Lithium ion anode material lithium supplement additive and preparation method thereof
CN113809419A (en) * 2021-09-14 2021-12-17 远景动力技术(江苏)有限公司 Formation method and formed lithium ion battery
WO2022007021A1 (en) * 2020-07-09 2022-01-13 湖北融通高科先进材料有限公司 Carbon-coated lithium-rich oxide composite material and preparation method therefor
CN114497694A (en) * 2021-12-29 2022-05-13 天津先众新能源科技股份有限公司 Lithium supplement agent for manufacturing lithium ion battery and preparation method thereof
CN114497514A (en) * 2022-03-15 2022-05-13 远景动力技术(江苏)有限公司 Positive electrode lithium supplement agent and application thereof
CN114709391A (en) * 2022-04-01 2022-07-05 湖北亿纬动力有限公司 Positive electrode lithium supplement material, preparation method thereof and lithium ion battery
CN115000362A (en) * 2022-04-29 2022-09-02 中南大学 Li 5 Fe x M y O 4 @ C composite material, preparation thereof and application thereof in lithium ion battery
CN115676895A (en) * 2022-11-09 2023-02-03 山东海科创新研究院有限公司 Lithium-rich lithium iron oxide and synthesis method thereof
WO2023142666A1 (en) * 2022-01-27 2023-08-03 广东邦普循环科技有限公司 Lithium ion battery pre-lithiation agent, preparation method therefor, and application
WO2023173775A1 (en) * 2022-03-18 2023-09-21 广东邦普循环科技有限公司 Modified lithium ion battery positive electrode material and preparation method therefor and application thereof
WO2024016445A1 (en) * 2022-07-21 2024-01-25 广东邦普循环科技有限公司 Carbon-coated lithium-rich oxide, and preparation method therefor and use thereof
WO2024016446A1 (en) * 2022-07-20 2024-01-25 广东邦普循环科技有限公司 Lithium-rich oxide with core-shell structure, and preparation method therefor and use thereof

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CN109817913A (en) * 2019-01-16 2019-05-28 江西中汽瑞华新能源科技有限公司 A kind of anode material for compound lithium ion battery and preparation method thereof
CN110048120A (en) * 2019-04-23 2019-07-23 王柯娜 A kind of preparation method of nanometer of ferrous acid lithium
CN112054166A (en) * 2019-06-06 2020-12-08 苏州第一元素纳米技术有限公司 Core-shell structure electrochemical active material, preparation method and battery
CN112054166B (en) * 2019-06-06 2021-08-06 苏州第一元素纳米技术有限公司 Core-shell structure electrochemical active material, preparation method and battery
CN110294494A (en) * 2019-07-25 2019-10-01 哈尔滨工业大学 Lithium vanadate anode mends lithium additive and its application
CN110294494B (en) * 2019-07-25 2022-04-01 哈尔滨工业大学 Lithium vanadate anode lithium supplement additive and application thereof
CN110459748A (en) * 2019-08-20 2019-11-15 湖北融通高科先进材料有限公司 A kind of carbon coating ferrous acid lithium material and preparation method thereof
CN110518223A (en) * 2019-09-06 2019-11-29 湖北融通高科先进材料有限公司 A kind of coating aluminium foil and preparation method thereof
CN112490415B (en) * 2019-09-12 2022-06-28 巴斯夫杉杉电池材料有限公司 Lithium ion anode material lithium supplement additive and preparation method thereof
CN112490415A (en) * 2019-09-12 2021-03-12 湖南杉杉能源科技股份有限公司 Lithium ion anode material lithium supplement additive and preparation method thereof
WO2022007021A1 (en) * 2020-07-09 2022-01-13 湖北融通高科先进材料有限公司 Carbon-coated lithium-rich oxide composite material and preparation method therefor
CN111769288A (en) * 2020-08-13 2020-10-13 哈尔滨工业大学 Method for in-situ lithium supplement of lithium ion battery anode material
CN111769288B (en) * 2020-08-13 2022-05-03 哈尔滨工业大学 Method for in-situ lithium supplement of lithium ion battery anode material
CN112117433A (en) * 2020-09-01 2020-12-22 深圳市德方纳米科技股份有限公司 Preparation method of lithium ferrite
CN112117136A (en) * 2020-09-14 2020-12-22 东北石油大学 GO-CS coated potassium ferrate material and preparation method and application thereof
CN112117136B (en) * 2020-09-14 2021-09-14 东北石油大学 GO-CS coated potassium ferrate material and preparation method and application thereof
CN112164796A (en) * 2020-09-16 2021-01-01 合肥国轩高科动力能源有限公司 Pre-lithiation additive for positive electrode material of lithium ion battery and preparation method and application thereof
CN113809419A (en) * 2021-09-14 2021-12-17 远景动力技术(江苏)有限公司 Formation method and formed lithium ion battery
CN114497694A (en) * 2021-12-29 2022-05-13 天津先众新能源科技股份有限公司 Lithium supplement agent for manufacturing lithium ion battery and preparation method thereof
WO2023142666A1 (en) * 2022-01-27 2023-08-03 广东邦普循环科技有限公司 Lithium ion battery pre-lithiation agent, preparation method therefor, and application
GB2620047A (en) * 2022-01-27 2023-12-27 Guangdong Brunp Recycling Technology Co Ltd Lithium ion battery pre-lithiation agent, preparation method therefore, and application
CN114497514A (en) * 2022-03-15 2022-05-13 远景动力技术(江苏)有限公司 Positive electrode lithium supplement agent and application thereof
WO2023173775A1 (en) * 2022-03-18 2023-09-21 广东邦普循环科技有限公司 Modified lithium ion battery positive electrode material and preparation method therefor and application thereof
CN114709391A (en) * 2022-04-01 2022-07-05 湖北亿纬动力有限公司 Positive electrode lithium supplement material, preparation method thereof and lithium ion battery
CN115000362A (en) * 2022-04-29 2022-09-02 中南大学 Li 5 Fe x M y O 4 @ C composite material, preparation thereof and application thereof in lithium ion battery
CN115000362B (en) * 2022-04-29 2024-06-11 中南大学 Li5FexMyO4@C composite material, preparation method thereof and application thereof in lithium ion battery
WO2024016446A1 (en) * 2022-07-20 2024-01-25 广东邦普循环科技有限公司 Lithium-rich oxide with core-shell structure, and preparation method therefor and use thereof
WO2024016445A1 (en) * 2022-07-21 2024-01-25 广东邦普循环科技有限公司 Carbon-coated lithium-rich oxide, and preparation method therefor and use thereof
CN115676895A (en) * 2022-11-09 2023-02-03 山东海科创新研究院有限公司 Lithium-rich lithium iron oxide and synthesis method thereof

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