CN109616629B - Lithium-supplementing positive electrode active material, positive electrode material, lithium ion battery, and preparation and application of lithium-supplementing positive electrode active material - Google Patents

Lithium-supplementing positive electrode active material, positive electrode material, lithium ion battery, and preparation and application of lithium-supplementing positive electrode active material Download PDF

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CN109616629B
CN109616629B CN201811420709.1A CN201811420709A CN109616629B CN 109616629 B CN109616629 B CN 109616629B CN 201811420709 A CN201811420709 A CN 201811420709A CN 109616629 B CN109616629 B CN 109616629B
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lithium
positive electrode
active material
supplementing
supplement
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CN109616629A (en
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张治安
赖延清
王大鹏
胡均贤
王鹏程
郭琪
吴漫东
宋佳惠
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Hunan Fengyuan Yeshine Kingco New Energy Co ltd
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Central South University
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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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

The invention belongs to the field of lithium ion battery materials, and particularly discloses a lithium supplement anode active material which comprises an anode active material and at least one lithiated organic lithium supplement agent. The invention also discloses a lithium supplement anode material containing the lithium supplement anode active material, a lithium supplement anode and a lithium ion battery loaded by adopting the lithium supplement anode. The invention discovers that the lithium supplement additive and the positive active material are synergistic, and in addition, the invention also provides a preparation method which is simple to operate, short in preparation period and high in product activity.

Description

Lithium-supplementing positive electrode active material, positive electrode material, lithium ion battery, and preparation and application of lithium-supplementing positive electrode active material
Technical Field
The invention belongs to the field of energy storage devices, and particularly relates to a lithium-supplement positive electrode active material, and preparation and application thereof.
Background
Lithium Ion Batteries (LIBs) currently have the most promising and fastest-developing high-efficiency secondary batteries, and have the advantages of high specific energy, low self-discharge, good cycle performance, no memory effect and the like. Li in lithium ion batteries+From the positive electrode material, the negative electrode surface of a lithium ion battery consumes Li during the first charge of the battery+An SEI film is formed, resulting in a Loss of first charge and discharge Capacity (ICL). With the continuous development of lithium ion batteries, high-capacity silicon cathode materials are gradually applied to the lithium ion batteries, but the ICL of the silicon cathode is as high as 50-70%. Therefore, it is of great significance to develop a simple and efficient lithium supplement technology.
The current Lithium supplement scheme mainly comprises the Lithium supplement of the negative electrode, for example, c.r.jarvis adopts Stabilized Lithium Metal Powder (SLMP) produced by FMC corporation to mix with graphite material to prepare slurry, the slurry is coated on the surface of a copper current collector to prepare the negative electrode, and electrolyte (1.2M LiPF) is injected6EC/EMC) and AG particles, in which Li is spontaneously dissolved, Li+The lithium ion is transferred and inserted into the graphite negative electrode to achieve the purpose of lithium supplement of the graphite negative electrode (Journal of Power Sources, 2006, 162 (2): 800-. But has the problems of uncontrollable lithium intercalation current, extremely high requirement on the production process, potential safety hazard, difficulty in continuous production and the like.
The lithium supplement of the positive electrode and the lithium supplement of the negative electrode are completely different technical fields, and are a brand new lithium supplement idea, and the lithium supplement idea utilizes a positive electrode material to fill irreversible Li generated at the negative electrode+And thus the ICL of the entire battery is reduced.
The anode lithium supplement material reported in the prior art is mainly Li5FeO4. For example, Xin Su utilizes Li5FeO4Additive used as anode material and LiCoO2Mixing as a common positive electrode showed addition of 7 wt% Li5FeO4After the initial charging to 4.3V, 233mAh/g of capacity can be obtained, and the reversible capacity of the full battery formed by the hard carbon cathode is improved by 14% (Journal of Power Sources, 2016, 324: 150-. However, the method has the problems that the synthesis is difficult, materials after reaction can remain in the positive electrode and have adverse effects on the overall performance of the battery, and the like; other materials such as Li2And gas is generated after the reaction of O and the like, so that potential safety hazards are caused.
In summary, the lithium supplementing performance, safety, stability and production continuity of the positive electrode lithium supplementing material still need to be further improved.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, a first object of the present invention is to provide a lithium-supplementing cathode active material as a lithium supplementing agent, which aims to supplement lithium to a cathode of a lithium ion battery and improve the performance of an electrode material.
The second purpose of the present invention is to provide a lithium-supplementing cathode material containing the organic lithium salt of the present invention, which aims to significantly improve the electrical properties of the cathode material obtained by compounding the additive and the cathode active material.
The third purpose of the invention is to provide a preparation method of the lithium supplement cathode material.
The fourth purpose of the invention is to provide an application of the lithium supplement cathode material in the preparation of a lithium ion battery.
A fifth object of the present invention is to provide a lithium ion battery to which the lithium-supplementing positive electrode material is added.
A lithium-supplementing cathode active material comprises a cathode active material and at least one organic lithium supplementing agent with a structural formula of formula 1;
Figure BDA0001879440580000021
said R1is-F, -Cl, -COOH, -CN or-NO2；
Said R2～R5independently-OLi or H; wherein R is2～R5In (A), at least one substituent is-OLi.
The inventor innovatively finds that the organic lithium supplement agent with the structure of formula 1 and the positive active material have good cooperativity, so that the lithium supplement positive active material has good positive lithium supplement activity, the loss of first charge-discharge capacity is reduced, and the first charge-discharge efficiency of the lithium ion battery is improved. The inventor unexpectedly finds that after the organic lithium supplementing agent is used for supplementing lithium and removing lithium ions, the rest part can be spontaneously dissolved into electrolyte, and the negative influence on the positive plate can not be caused.
The inventor researches and discovers that R is controlled2～R5The number of the substituent groups of-OLi in the formula is beneficial to controlling the lithium supplementing effect and regulating and controlling the first charge and discharge efficiency of the lithium ion battery.
Preferably, R2～R5Two to three substituents in (A) are-OLi. The research shows that in the preferable range, the lithium-supplementing positive electrode active material has better electrical effect. It has also been found that higher-OLi substitution numbers or lower-OLi substitution numbers all affect the electrical performance to some extent. When the number of-OLi substitutions is higher than three, the rate at which the capacity will increase as the number of substitutions increases will be slowed.
Further preferably, R2～R5Three substituents in (a) are-OLi. Research shows that when the three substituents in the formula 1 are OLi, the synergistic effect of the three substituents and the positive electrode active material is better, and the lithium-supplement positive electrode active material can show better electrical properties.
Preferably, the lithium supplement agent is at least one of a compound shown in a formula 1-a and a compound shown in a formula 1-b;
Figure BDA0001879440580000031
it is found that in formula 1, R2、R3、R5is-OLi; r4、R6Is H; or, R2、R4、R5is-OLi; r3、R6Is H. The organic lithium supplement agent and the positive electrode active material at the substitution position have better synergistic effect.
The inventor innovatively finds that when the number of hydroxyl groups is the same, the organic lithium supplement agents at different hydroxyl positions are mixed and are used together with the positive active material, so that the good cooperativity is achieved, the positive lithium supplement effect can be achieved, an SEI (solid electrolyte interphase) film can be formed on a negative electrode, the stability of the material is improved, and besides, the electrical property can be obviously improved in a cooperative manner, and the first charge-discharge coulomb efficiency is improved.
The research also finds that the lithium supplement agent comprises a compound shown in a formula 1-a and a compound shown in a formula 1-b. The combined use of formula 1-a and formula 1-b has an unexpected synergistic effect. The synergistic organic lithium supplement agent is used together with the positive active material, has good cooperativity and better positive lithium supplement effect, is beneficial to forming an SEI film on a negative electrode, obviously synergistically promotes electrical properties, and improves the first charge-discharge coulombic efficiency. In addition, the stability of the material is improved.
Further preferably, in the compounds of formula 1-a and 1-b, R1is-NO2. Preferably R1The following compound organic lithium supplement agent can further improve the cooperativity of the two.
More preferably, in the lithium supplement agent, the mass ratio of the compound of the formula 1-a to the compound of the formula 1-b is 1-5: 1-5.
The organic lithium supplement agent is obtained by carrying out lithiation reaction on a precursor raw material for synthesizing the organic lithium supplement agent and a lithiation reagent, and then carrying out solid-liquid separation and vacuum drying.
Preferably, the precursor raw material is a compound obtained by reacting-F, -Cl, -COOH, -CN or-NO at one position on a benzene ring2Substituted, with at least one other position substituted with a hydroxy group.
Preferably, the solvent for lithiation reaction is one or more of N, N-dimethylformamide, tetrahydrofuran, ethylene carbonate, diethyl carbonate and methyl ethyl carbonate.
Preferably, the lithiation reagent is one or more of lithium hydride, lithium nitride, lithium acetylide and metal lithium powder.
Preferably, the lithiating agent is used in an amount not less than the theoretical molar amount for complete lithiation of the-OH groups (including phenolic and carboxyhydroxylic groups on the benzene ring) in the precursor feedstock; preferably 1 to 1.2 times of theoretical molar weight; more preferably 1.05 to 1.1. The research shows that the product and the positive active material prepared under the control of the range, particularly the preferable range, have better synergistic effect; can synergistically show better lithium supplementing effect. Research also finds that the dosage of the lithiation reagent is further increased, but the lithium supplementing performance of the product is not improved.
The temperature during the lithiation reaction is room temperature, for example, 15 to 40 ℃.
The lithiation reaction is carried out under stirring, and the preferred stirring speed is 200-400 rpm.
Preferably, the lithiation reaction time is 6-12 h.
Preferably, the temperature of vacuum drying is 100-150 ℃; the time is preferably 1 to 3 hours.
The organic lithium supplement agent prepared by the method and the positive active material can synergistically improve the lithium supplement effect.
In the present invention, a more preferred positive electrode active material is LiCoO2、LiFePO4And at least one of nickel-cobalt-manganese ternary materials.
Preferably, the weight ratio of the organic lithium supplement agent to the positive electrode active material is 2-10: 70-78. It has been found that controlling the amount to be within the preferred range contributes to further improving the synergistic lithium replenishment effect of the lithium replenishment positive electrode active material.
The invention also provides a lithium ion battery lithium-supplementing cathode material which comprises the lithium-supplementing cathode active material, a binder and a conductive agent.
Researches find that the lithium supplement cathode material has a good first lithium supplement effect and can remarkably improve the first charge-discharge efficiency of the battery.
Preferably, in the lithium supplement cathode material, the content of the organic lithium supplement agent is 2-10 wt%. Research shows that the electrical property of the lithium supplement cathode material can be further improved and the first charge-discharge coulombic efficiency can be improved by controlling the content of the organic lithium supplement agent in the preferable range.
The conductive agent can be a material which can be recognized in the industry and can be used for the positive electrode and has conductive performance; for example, at least one of acetylene black and ketjen black.
Preferably, in the lithium-supplement cathode material, the content of the conductive agent is 5-10 wt%.
The binder can be a material which can be used for mutually binding the positive pole components and can be recognized in the industry; for example, at least one of PVDF and PTFE may be used.
Preferably, in the lithium-supplement cathode material, the percentage content of the binder is 5-10 wt%.
The invention also provides a preparation method of the lithium-supplementing cathode material, firstly, the organic lithium-supplementing agent is prepared by the method, and then the lithium-supplementing cathode material is prepared by the organic lithium-supplementing agent, the cathode active material and the additive components (such as a conductive agent and a binding agent) which are allowed to be added for preparing the cathode material.
The invention also discloses an application of the lithium-supplement cathode material: the lithium ion battery positive electrode is used for preparing a positive electrode plate (also called as a positive electrode) of a lithium ion battery.
Preferably, the lithium-supplement positive electrode material is applied to the preparation of a lithium ion battery by using the prepared positive electrode piece.
Preferably, the lithium ion battery is obtained by assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte.
The application of the lithium-supplement cathode material specifically comprises the following steps: the method comprises the steps of uniformly mixing a positive active material, an organic lithium supplement agent, a conductive agent and a binder, then carrying out subsequent treatment to obtain a positive pole piece of the lithium ion battery, uniformly mixing a negative active material, a conductive agent and a binder, then carrying out subsequent treatment to obtain a negative pole piece of the lithium ion battery, assembling the positive pole piece and the negative pole piece, and then carrying out activation treatment to realize lithium supplement of the negative pole piece to obtain the lithium ion battery.
Preferably, the negative active material is one or more of graphite, hard carbon and silicon carbon material.
Preferably, in the positive pole piece, the mass of the organic lithium supplement agent is 2-10% of the total mass of the lithium supplement positive pole material, and the mass of the conductive agent and the binder are respectively 5-10% of the mass of the lithium supplement positive pole material; in the negative pole piece, the total mass of the conductive agent and the binder is 5-10% of the mass of the negative pole material.
Preferably, the first charge capacity of the organic lithium supplement agent is 300-700 mAh.g-1The first charge-discharge efficiency is 1-10%.
The lithium supplement anode material is applied to lithium supplement treatment of an assembled lithium ion battery, preferably, the lithium supplement treatment is performed through one-time charge-discharge circulation, the first charge adopts 0.02-0.1C for constant-current or constant-voltage charge, the cut-off voltage is 4.0-4.5V, the first discharge adopts 0.02-0.1C for constant-current discharge, and the cut-off voltage is 1.5-2.0V. The lithium in the material can be completely removed by adopting small current during charging, and the material structure can be damaged by adopting large current during discharging, so that the lithium can not be removed.
The invention also provides a lithium ion battery lithium supplement anode which comprises an anode current collector and the lithium ion battery lithium supplement anode material compounded on the surface of the anode current collector.
The lithium ion battery lithium-supplement anode can be prepared by the existing method, the lithium-supplement anode material is slurried by using a solvent, and then the slurry is coated on an anode current collector, dried and sliced to obtain the lithium ion battery lithium-supplement anode.
The invention also provides a lithium ion battery assembled by the lithium-supplement cathode material as a general technical concept. The first charge-discharge coulombic efficiency of the lithium ion battery is 90-99%.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the high-capacity organic lithium supplement agent is used for supplementing lithium to the negative electrode of the lithium battery, so that the problem of capacity loss of the battery in the first charging and discharging process can be effectively reduced, and the energy density and the cycle performance of the whole battery are improved.
2. Aiming at the problem that gas is generated in the process of preparing the traditional lithium supplementing material or remains in the anode after reaction, the organic lithium supplementing agent is adopted for lithium supplementation, and the residual organic part after lithium removal is dissolved in the electrolyte, so that the residual organic part cannot remain in the anode or generate gas.
3. According to the invention, lithium salts at different hydroxyl positions are compounded by controlling the synthesis conditions of the organic lithium supplement agent, so that the lithium supplement material with higher specific capacity and lower reversible capacity is obtained.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below. Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a preparation method of a lithium ion battery for supplementing lithium by using an organic lithium supplementing agent (also called organic lithium salt) and comprises the following steps:
1. preparation of organic lithium salt:
(1) lithium acetylide ((Li) was weighed in a molar ratio of 1.5: 1)2C2) And 2, 3, 5-trihydroxynitrobenzene were dispersed in the organic solvent and stirred at 200rpm for 6 h.
(2) Carrying out suction filtration on the turbid liquid obtained in the step (1), and carrying out vacuum drying on a filter cake at 100 ℃ for 1h to obtain the product with the first charge capacity of 400 mAh.g-1Lithiated 2, 3, 5-trihydroxynitrobenzene with a first charge-discharge efficiency of 10%.
2. Subjecting LiCoO to condensation2(70 wt%), lithiated 2, 3, 5-trihydroxy nitrobenzene (10 wt%), Super P (10 wt%) and PVDF (10 wt%) are uniformly mixed, and then slurry mixing, coating, drying and rolling are carried out to obtain the positive pole piece.
3. And uniformly mixing the hard carbon (90 wt%), the Super P (5 wt%) and the PVDF (5 wt%), and then carrying out size mixing, coating, drying and rolling to obtain the negative pole piece.
4. And assembling the positive and negative pole pieces to obtain the lithium ion battery, and realizing lithium supplement of the negative pole material in the first charge-discharge cycle. Wherein the first charge-discharge cycle conditions are as follows:
table 1: first charge-discharge cycle conditions in example 1:
circulation of Initial voltage Cut-off voltage Mechanism for controlling a motor
First time charging OCV 4.5V Constant current charging (0.02C)
First discharge 4.5V 2.0V Constant current discharge (0.02C)
The first charge-discharge efficiency of the lithium ion battery assembled in the example was determined to be 91.2%.
Example 2:
a preparation method of a lithium ion battery adopting an organic lithium supplementing agent and organic lithium salt for supplementing lithium comprises the following steps:
1. preparation of organic lithium salt:
(1) lithium acetylide and 2, 3, 5-trihydroxy nitrobenzene with the molar ratio of 1.6: 1 are weighed and dispersed in the organic solvent and stirred, the stirring speed is 250rpm, and the stirring time is 8 hours.
(2) Carrying out suction filtration on the turbid liquid obtained in the step (1), and carrying out vacuum drying on a filter cake at 110 ℃ for 1.5h to obtain the product with the first charge capacity of 436mAh g-1Lithiation 2, 3, 5-trihydroxynitrobenzene with a first charge-discharge efficiency of 8%.
2. Subjecting LiCoO to condensation2(73wt％)、Li2And uniformly mixing DHBN (7 wt%), Super P (10 wt%) and PVDF (10 wt%), and then carrying out size mixing, coating, drying and rolling to obtain the positive pole piece.
3. And uniformly mixing the hard carbon (90 wt%), the Super P (5 wt%) and the PVDF (5 wt%), and then carrying out size mixing, coating, drying and rolling to obtain the negative pole piece.
4. And assembling the positive and negative pole pieces to obtain the lithium ion battery, and realizing lithium supplement of the negative pole material in the first charge-discharge cycle. Wherein the first charge-discharge cycle conditions are as follows:
table 2: first charge-discharge cycle conditions in example 2:
circulation of Initial voltage Cut-off voltage Mechanism for controlling a motor
First time charging OCV 4.5V Constant current charging (0.05C)
First discharge 4.5V 2.0V Constant current discharge (0.05C)
Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the example is 92.4%.
Example 3:
a preparation method of a lithium ion battery adopting an organic lithium supplementing agent and organic lithium salt for supplementing lithium comprises the following steps:
1. preparation of organic lithium salt:
(1) lithium acetylide and 2, 3, 5-trihydroxy nitrobenzene with the molar ratio of 1.65: 1 are weighed and dispersed in the organic solvent and stirred, the stirring speed is 300rpm, and the stirring time is 9 hours.
(2) Carrying out suction filtration on the turbid liquid obtained in the step (1), and carrying out vacuum drying on a filter cake at 120 ℃ for 2h to obtain the product with the primary charge capacity of 456mAh g-1Lithiation 2, 3, 5-trihydroxynitrobenzene with a first charge-discharge efficiency of 6%.
2. Subjecting LiCoO to condensation2(75 wt%), lithiated 2, 3, 5-trihydroxy nitrobenzene (5 wt%), Super P (10 wt%) and PVDF (10 wt%) are uniformly mixed, and then slurry mixing, coating, drying and rolling are carried out to obtain the positive pole piece.
3. And uniformly mixing the hard carbon (90 wt%), the Super P (5 wt%) and the PVDF (5 wt%), and then carrying out size mixing, coating, drying and rolling to obtain the negative pole piece.
4. And assembling the positive and negative pole pieces to obtain the lithium ion battery, and realizing lithium supplement of the negative pole material in the first charge-discharge cycle. Wherein the first charge-discharge cycle conditions are as follows:
table 3: first charge-discharge cycle conditions in example 3:
circulation of Initial voltage Cut-off voltage Mechanism for controlling a motor
First time charging OCV 4.5V Constant current charging (0.05C)
First discharge 4.5V 2.0V Constant current discharge (0.05C)
The first charge-discharge efficiency of the lithium ion battery assembled in the example was determined to be 93.1%.
Example 4:
a preparation method of a lithium ion battery adopting an organic lithium supplementing agent and organic lithium salt for supplementing lithium comprises the following steps:
1. subjecting LiCoO to condensation2(75 wt%), lithiated 2, 3, 5-trihydroxy nitrobenzene (4 wt%), lithiated 2, 4, 5-trihydroxy nitrobenzene (1 wt%), Super P (10 wt%) and PVDF (10 wt%) prepared in example 3 were mixed uniformly, and then slurry mixing, coating, drying and rolling were carried out to obtain a positive electrode plate.
2. And uniformly mixing the hard carbon (90 wt%), the Super P (5 wt%) and the PVDF (5 wt%), and then carrying out size mixing, coating, drying and rolling to obtain the negative pole piece.
3. And assembling the positive and negative pole pieces to obtain the lithium ion battery, and realizing lithium supplement of the negative pole material in the first charge-discharge cycle. Wherein the first charge-discharge cycle conditions are as follows:
table 4: first charge-discharge cycle conditions in example 4:
circulation of Initial voltage Cut-off voltage Mechanism for controlling a motor
First time charging OCV 4.5V Constant current charging (0.05C)
First discharge 4.5V 2.0V Constant current discharge (0.05C)
Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the example is 94.0%.
Example 5:
a preparation method of a lithium ion battery adopting an organic lithium supplementing agent and organic lithium salt for supplementing lithium comprises the following steps:
1. subjecting LiCoO to condensation2(75 wt%), lithiated 2, 3, 5-trihydroxynitrobenzene (3.5 wt%), lithiated 2, 4, 5-trihydroxynitrobenzene (1.5 wt%), Super P (10 wt%) and PVDF (10 wt%) prepared in example 3 were mixed uniformly, and then slurry mixing, coating, drying and rolling were carried out to obtain a positive electrode plate.
2. And uniformly mixing the hard carbon (90 wt%), the Super P (5 wt%) and the PVDF (5 wt%), and then carrying out size mixing, coating, drying and rolling to obtain the negative pole piece.
3. And assembling the positive and negative pole pieces to obtain the lithium ion battery, and realizing lithium supplement of the negative pole material in the first charge-discharge cycle. Wherein the first charge-discharge cycle conditions are as follows:
table 5: first charge-discharge cycle conditions in example 5:
circulation of Initial voltage Cut-off voltage Mechanism for controlling a motor
First time charging OCV 4.5V Constant current charging (0.05C)
First discharge 4.5V 2.0V Constant current discharge (0.05C)
Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the example is 93.9%.
Examples 6 to 9:
1. subjecting LiCoO to condensation2(75 wt%), the organic lithium supplement agent (5 wt%), the Super P (10 wt%) and the PVDF (10 wt%) which are described in the table 6 are uniformly mixed, and then the positive pole piece is obtained through size mixing, coating, drying and rolling.
2. And uniformly mixing the hard carbon (90 wt%), the Super P (5 wt%) and the PVDF (5 wt%), and then carrying out size mixing, coating, drying and rolling to obtain the negative pole piece.
3. And assembling the positive and negative pole pieces to obtain the lithium ion battery, and realizing lithium supplement of the negative pole material in the first charge-discharge cycle. Wherein the first charge-discharge cycle conditions were the same as in example 1. The first charge-discharge efficiency test data of the assembled lithium ion battery are shown in Table 6
TABLE 6
Figure BDA0001879440580000091
Figure BDA0001879440580000101
Comparative example 1:
compared with example 1, the difference is only, in 2, LiCoO2After 80 wt%, Super P (10 wt%) and PVDF (10 wt%) are uniformly mixed, the positive pole piece is obtained through size mixing, coating, drying and rolling.
Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the comparative example is 81.9%. Since no Li is added2DHBN，LiCoO2Li in (1)+The loss of the graphite cathode results in low first charge-discharge efficiency.
Comparative example 2:
compared with example 1, the difference is only, in 2, LiCoO255 wt%, lithiation 2, 3, 5-trihydroxy nitrobenzene (25 wt%), Super P (10 wt%) and PVDF (10 wt%) are uniformly mixed, and then slurry mixing, coating, drying and rolling are carried out, so as to obtain the positive pole piece.
Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the comparative example is 77.1%. Because the additive lithiates the 2, 3, 5-trihydroxy nitrobenzene, the first charge-discharge efficiency is very low, and when the addition amount of the additive is increased, key factors limiting the first charge-discharge efficiency of the whole battery are converted from a negative electrode to a positive electrode.
Comparative example 3:
compared with example 1, the difference is only, in 2, LiCoO279.5 wt%, lithiated 2, 3, 5-trihydroxy nitrobenzene (0.5 wt%), Super P (10 wt%) and PVDF (10 wt%) are uniformly mixed, and then the positive pole piece is obtained through size mixing, coating, drying and rolling.
Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the comparative example is 81.9%. Due to the additive Li2The amount of DHBN is small and therefore it gives rise to more Li+The ICL on the graphite cathode is not supplemented enough, so that the first charge-discharge efficiency of the battery is not obviously improved.
Comparative example 4:
the only difference compared to example 1 is that in step (1), the stirring time was 3 h. Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the comparative example is 86.6%. Since the reaction time was short and the reaction of the raw materials was incomplete, the effect of lithium supplementation was not as good as in example 1.
Comparative example 5:
the only difference compared to example 1 is that in step (2), no vacuum drying was used. Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the comparative example is 86.4%. Because vacuum drying is not adopted, part of the organic lithium supplement agent lithiates 2, 3, 5-trihydroxynitrobenzene to react with water vapor to generate 3, 4-dihydroxybenzonitrile, and then the performance of the organic lithium supplement agent is influenced.
Comparative example 6:
compared with example 4, the difference is only that LiCoO is used in 12(75 wt%), lithiated 2, 3, 5-trihydroxy nitrobenzene (4 wt%), lithiated P-hydroxyl nitrobenzene (1 wt%), Super P (10 wt%) and PVDF (10 wt%) prepared in example 3 were mixed uniformly, and then slurry mixing, coating, drying and rolling were carried out to obtain a positive electrode plate.
Through determination, the first charge-discharge efficiency of the lithium ion battery assembled in the comparative example is 91.9%. The lithium supplementing effect of the additive is relatively reduced because the lithiation capacity of the additive is lower than that of hydroxyl nitrobenzene.

Claims (14)

1. The lithium supplement positive active material is characterized by comprising a positive active material and an organic lithium supplement agent;
the organic lithium supplement agent comprises a compound shown in a formula 1-a and a compound shown in a formula 1-b;
Figure 633312DEST_PATH_IMAGE001
Figure 19294DEST_PATH_IMAGE002
formula 1-a formula 1-b;
wherein, R is1is-F, -Cl, -COOH, -CN or-NO2。
2. The lithium-supplementing positive electrode active material according to claim 1, wherein the organic lithium-supplementing agent has a mass ratio of the compound of formula 1-a to the compound of formula 1-b of 1 to 5: 1 to 5.
3. The lithium-supplementing positive electrode active material according to claim 1, wherein the positive electrode active material is LiCoO2、LiFePO4And at least one of nickel-cobalt-manganese ternary materials.
4. The lithium-supplementing positive electrode active material according to any one of claims 1 to 3, wherein the weight ratio of the organic lithium-supplementing agent to the positive electrode active material is 2 to 10: 70-78.
5. The lithium-supplementing positive electrode active material as claimed in claim 1, wherein the organic lithium-supplementing agent is obtained by carrying out lithiation reaction on a precursor raw material for synthesizing the organic lithium-supplementing agent and a lithiation reagent, and then carrying out solid-liquid separation and vacuum drying.
6. The lithium-supplementing positive electrode active material according to claim 5, wherein a solvent for the lithiation reaction is one or more of N, N-dimethylformamide, tetrahydrofuran, ethylene carbonate, diethyl carbonate, and methylethyl carbonate.
7. The lithium-supplementing positive electrode active material according to claim 5, wherein the lithiation agent is at least one of lithium hydride, lithium nitride, lithium acetylide, and metallic lithium powder.
8. The lithium-replenishing positive electrode active material according to claim 5, wherein the lithiating agent is used in an amount not less than a theoretical molar amount for complete lithiation of-OH in the precursor raw material.
9. The lithium-supplementing positive electrode active material according to claim 5, wherein the lithiation reaction time is 6 to 12 hours.
10. The lithium-supplementing positive electrode active material according to claim 5, wherein the temperature of vacuum drying is 100 to 150 ℃; the time is 1-3 h.
11. A lithium ion battery lithium supplement positive electrode material, characterized by comprising the lithium supplement positive electrode active material according to any one of claims 1 to 10, and further comprising a binder and a conductive agent.
12. The lithium ion battery lithium supplement cathode material according to claim 11, wherein the lithium supplement cathode material contains 2-10 wt% of an organic lithium supplement agent; the content of the conductive agent is 5-10 wt%; the content of the binder is 5-10 wt%; the balance being positive active material.
13. The lithium ion battery lithium supplement positive electrode is characterized by comprising a positive electrode current collector and the lithium ion battery lithium supplement positive electrode material of claim 11 or 12 compounded on the surface of the positive electrode current collector.
14. A lithium ion battery comprising the lithium-supplementing positive electrode according to claim 13 as a positive electrode.
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