CN112018388A - Lithium ion battery anode additive and preparation method thereof, lithium ion battery anode and lithium ion battery - Google Patents

Lithium ion battery anode additive and preparation method thereof, lithium ion battery anode and lithium ion battery Download PDF

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Publication number
CN112018388A
CN112018388A CN201910472964.9A CN201910472964A CN112018388A CN 112018388 A CN112018388 A CN 112018388A CN 201910472964 A CN201910472964 A CN 201910472964A CN 112018388 A CN112018388 A CN 112018388A
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additive
weight
parts
lithium ion
positive electrode
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CN112018388B (en
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焦晓朋
李世彩
韩晓燕
胡栋杰
江正福
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BYD Co Ltd
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BYD 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 disclosure relates to a lithium ion battery anode additive, a preparation method thereof, a lithium ion battery anode and a lithium ion battery, wherein the additive is Ni2O3And Li2CO3Wherein Li is based on 100 parts by weight of the additive2CO3In an amount of 10 to 95 parts by weight, Li2CO3Has an average particle diameter of 50nm to 20 μm, Ni2O3Has an average particle diameter of 50nm to 5 μm. The positive electrode additive has low decomposition voltage, and contains the positive electrode additiveThe lithium ion battery added with the agent has good structural stability and cycling stability.

Description

Lithium ion battery anode additive and preparation method thereof, lithium ion battery anode and lithium ion battery
Technical Field
The disclosure relates to the field of lithium ion batteries, in particular to a lithium ion battery anode additive and a preparation method thereof, a lithium ion battery anode and a lithium ion battery.
Background
The SEI film is a passivation layer covering the surface of an electrode material formed by the reaction of the electrode material and an electrolyte on a solid-liquid phase interface in the first charge-discharge process of the liquid lithium ion battery. The formed passivation film can effectively prevent solvent molecules from passing through, but Li+But can be freely inserted and extracted through the passivation layer, and has the characteristics of a solid electrolyte, so that the passivation film is called a "solid electrolyte interface film" (SEI film for short). But the negative electrode consumes a part of active lithium to form the SEI film, resulting in a decrease in the first cycle efficiency of the negative electrode.
Document "Electrochemical decomposition of Li2CO3in NiO-Li2CO3The nanocomposite lithium film and powder electrodes' discloses a lithium supplement material capable of supplementing lithium to a lithium ion battery, but the material can only play a role when the voltage is higher than 4.4V, and thus for a positive electrode material, particularly a ternary material, the higher the charging voltage is, the larger the irreversible change of the positive electrode structure is, and the structural stability and the cycle performance of the lithium ion battery are seriously influenced.
Disclosure of Invention
The invention aims to overcome the problems of active lithium loss, unstable structure and poor cycle performance of a lithium ion battery in the first charging process, and provides a lithium ion battery anode additive, a preparation method thereof, a lithium ion battery anode and a lithium ion battery.
In order to achieve the above object, the present disclosure provides, in a first aspect, a lithium ion battery positive electrode additive, which is Ni2O3And Li2CO3Wherein the Li is based on 100 parts by weight of the additive2CO3In an amount of 10 to 95 parts by weight, said Li2CO3Has an average particle diameter of 50nm to 20 μm, and Ni2O3Has an average particle diameter of 50nm to 5 μm.
Optionally, the Li is based on 100 parts by weight of the additive2CO3In an amount of 40 to 50 parts by weight, the Li2CO3Has an average particle diameter of 100nm to 500nm, and Ni2O3Has an average particle diameter of 50nm to 200 nm.
Optionally, the Li is based on 100 parts by weight of the additive2CO3In an amount of 70 to 95 parts by weight, the Li2CO3Has an average particle diameter of 100nm to 500nm, and Ni2O3Has an average particle diameter of 50nm to 200 nm.
A second aspect of the present disclosure provides a method for preparing the lithium ion battery positive electrode additive provided by the first aspect of the present disclosure, the method comprising the steps of:
s1, mixing Ni2O3With Li2CO3Mixing to obtain a first material, wherein the Ni is added in an amount of 10 parts by weight2O3The Li2CO3The dosage of the compound is 1.1 to 190 weight portions;
s2, grinding the first material to obtain the additive;
alternatively, the method comprises the steps of:
a. mixing Ni2O3Mixing a soluble lithium source and a first solvent to obtain a second material;
b. mixing the soluble carbonate with a second solvent to obtain a third material;
c. and mixing and reacting the second material and the third material, and taking out a precipitate after reaction to obtain the additive.
Alternatively, in step S1, Ni2O3Has an average particle diameter of 50nm to 5 μm, and the Li2CO3The average particle diameter of (A) is 50nm-20 μm; in step S2, the grinding process is a ball milling process, the time of the ball milling process is 1-10 hours, and the rotation speed of the ball mill is 200-.
Optionally, step c further comprises: and taking out the precipitate in the third material, washing with a third solvent, and drying to obtain the additive, wherein the drying temperature is 50-150 ℃ and the drying time is 1-48 hours.
Optionally, in step a, relative to 10 parts by weight of Ni2O3The soluble lithium source is used in an amount of 0.7 to 355 parts by weight, the first solvent is used in an amount of 7 to 5100 parts by weight, and the Ni is used in an amount of2O3The average particle diameter of (A) is 50nm-5 μm; in step b, the soluble carbonate is used in an amount of 1.6 to 355 parts by weight relative to 10 parts by weight of the second material.
Optionally, the first solvent is selected from deionized water; the second solvent is selected from deionized water; the third solvent is selected from one or more of ethanol, methanol, propanol, acetone, diethyl ether and glycol; the soluble lithium source is selected from LiCl, LiOH, LiNO3、Li2SO4、Li2C2O4And CH3One or more of COOLi; the soluble carbonate is selected from K2CO3、Na2CO3And (NH)4)2CO3One or more of them.
A third aspect of the present disclosure provides a positive electrode for a lithium ion battery, comprising a positive active material, a positive current collector, and the positive electrode additive provided in the first aspect of the present disclosure.
Alternatively, the positive electrode additive may be contained in an amount of 0.05 to 2.5 parts by weight with respect to 10 parts by weight of the positive electrode active material.
A fourth aspect of the present disclosure provides a lithium ion battery including the lithium ion battery positive electrode provided by the third aspect of the present disclosure, a negative electrode, and an electrolyte.
By adopting the technical scheme, the lithium ion battery positive electrode additive disclosed by the invention is Ni with a specific proportion2O3And Li2CO3Mixed material of (2), Ni in the mixed material2O3As catalyst, Li2CO3Is an active material, wherein Ni2O3Catalytic Li2CO3And decomposing to generate lithium ions, thereby realizing lithium supplement to the lithium ion battery cathode. The positive electrode additive disclosed by the invention has a good lithium supplementing effect, and can ensure the cycle stability and the structural stability of the lithium ion battery.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is an XRD spectrum of the positive electrode additive prepared in example 1 and comparative example 4.
Fig. 2 is a charge-discharge curve diagram of batteries C1 and DC3 prepared in the positive electrode additive performance test at a charge-discharge rate of 0.1C.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
In a first aspect of the present disclosure, an additive for a positive electrode of a lithium ion battery is provided, wherein the additive is Ni2O3And Li2CO3Wherein the Li is based on 100 parts by weight of the additive2CO3In an amount of 10 to 95 parts by weight, the Li2CO3Has an average particle diameter of 50nm to 20 μm, and Ni2O3Has an average particle diameter of 50nm to 5 μm.
The lithium ion battery anode additive disclosed by the invention is Ni with a specific ratio2O3And Li2CO3The mixed material of (1), wherein, Ni2O3High activity and can catalyze Li2CO3The lithium ions are generated by decomposition under lower voltage and are transferred from the anode to the cathode, so that the cathode is supplemented in the first cycle process of the lithium ion battery to form SEActive lithium consumed in film I; and the charging voltage is lower in the process, and irreversible structural change of the positive active substance can be avoided, so that the lithium ion battery has excellent structural stability and cycling stability.
Specifically, Ni in the additives of the present disclosure2O3As catalyst, Li2CO3As active material, Li2CO3And Ni2O3The content ratio of (a) has an important influence on the performance of the lithium ion battery. When Li is present2CO3At a lower content of (D), Ni2O3Higher content of (C) is favorable for Li2CO3The mixed material with lower decomposition voltage can be obtained through decomposition, but the specific capacity of the mixed material is lower, and the lithium supplement effect of the mixed material as a positive electrode additive is influenced; when Li is present2CO3At higher contents of (2), Ni2O3Low content of (B) is not good for Li2CO3The decomposition voltage of the mixed material is higher, and the high decomposition voltage may cause the irreversible change of the structure of the positive electrode active material, thereby affecting the structural stability and the cycle performance of the lithium ion battery. Within the scope of the present disclosure, Li2CO3The content of the positive electrode additive is proper, the positive electrode additive has high specific capacity and low decomposition voltage, and structural change of a positive electrode active substance caused by high decomposition voltage of the additive can be effectively avoided, so that the lithium ion battery is ensured to have good structural stability and cycling stability.
Meanwhile, Li2CO3And Ni2O3Also has a significant impact on the performance of the lithium ion battery. When Li is present2CO3When the average particle diameter of (3) is too large, Li2CO3And Ni2O3The proportion of contact reaction is low, resulting in Li2CO3Slow decomposition so that Li2CO3Easy polarization to cut-off voltage and incomplete decomposition; when Li is present2CO3Is favorable for Li when the average particle diameter of (2) is small2CO3Decompose, but affect the specific capacity of the hybrid material. And Ni2O3Catalytic Li2CO3Generates lithium ions for the same mass of Ni2O3When being Ni2O3The larger the average particle diameter of (2), the smaller the specific surface area and the number of particles, and Li in contact therewith2CO3The smaller the particles are, the less detrimental to Li2CO3Decomposition of (2); when Ni is present2O3The smaller the average particle diameter of (2), the larger the specific surface area and the number of particles, and Li in contact therewith2CO3The more particles there are in favor of Li2CO3Decomposition of (3). Combining the above factors, when mixing Li in the material2CO3And Ni2O3When the average particle size is within the range, the lithium supplement efficiency of the additive is high, the effect is good, the specific capacity is high, and the lithium ion battery can further have better cycle stability and structural stability.
Preferably, the Li is based on 100 parts by weight of the additive2CO3May be contained in an amount of 40 to 50 parts by weight, the Li2CO3May have an average particle diameter of 100nm to 500nm, the Ni2O3The average particle diameter of (B) may be 50nm to 200 nm.
In accordance with the present disclosure, Li2CO3During decomposition, except for removing Li+In addition, CO is also produced2When the positive electrode additive of the present disclosure is used as a positive electrode additive for lithium supplementation, Li2CO3The material is decomposed to complete lithium supplement to the negative electrode during first charging, and generated CO2It escapes or is drawn out and does not remain in the battery. For example, when the lithium ion battery is charged for the first time, the liquid injection hole of the lithium ion battery can be unsealed, the lithium ion battery is placed in an inert atmosphere for charging, and gas generated during charging overflows from the liquid injection hole; or an air bag is left on the side edge when the lithium ion battery is manufactured, gas generated during charging is diffused into the air bag, the gas is extracted after the charging is finished, and then the side edge is molded. Li in the additive2CO3When the content of (b) is within the above range, the cycle stability and structural stability of the lithium ion battery can be further improved.The inventors of the present application have also found that CO is produced as a result of the additives of the present disclosure upon decomposition2Therefore, the lithium ion battery can also be used as a positive electrode additive for preventing overcharge. In this case Li2CO3Does not decompose during the first charging process, but decomposes to release CO when the battery is overcharged2The gas causes the pressure in the lithium ion battery to rise, and triggers a safety protection device (such as starting an explosion-proof valve), so that the thermal runaway caused by the overcharge of the anode material can be effectively prevented, and the overcharge safety of the battery is improved. Li in the additive2CO3When the content of (b) is within the above range, Li in the additive2CO3The decomposition voltage of (2) is below 4.3V, and the lithium iron phosphate battery can be used as a positive electrode additive for preventing overcharge of the lithium iron phosphate battery (the charge cut-off voltage is 3.8V). Meanwhile, Li in the above range2CO3And Ni2O3The average particle size of the lithium ion battery is appropriate, the average particle size of the lithium ion battery is matched with the average particle size of the lithium ion battery, so that the contact reaction efficiency of the lithium ion battery and the lithium ion battery is higher, the effect is better, and the cycle stability and the structural stability of the lithium ion battery can be further improved.
In accordance with the present disclosure, the Li is based on 100 parts by weight of the additive2CO3May be present in an amount of 70 to 95 parts by weight, the Li2CO3May have an average particle diameter of 100nm to 500nm, the Ni2O3The average particle diameter of (B) may be 50nm to 200 nm. Li in the additive2CO3When the content of (b) is within the above range, Li in the additive2CO3The decomposition voltage of the lithium ion battery is between 4.4 and 4.6V, and the lithium ion battery can be used as a positive electrode additive for preventing overcharge of a spinel lithium manganate lithium ion battery and/or a nickel cobalt lithium manganate lithium ion (ternary material) battery (the cut-off voltage is about 4.35V).
A second aspect of the present disclosure provides a method of preparing an additive provided by the first aspect of the present disclosure, the method comprising the steps of: s1, mixing Ni2O3With Li2CO3Mixing to obtain a first material, wherein the Ni is added in an amount of 10 parts by weight2O3The Li2CO3The dosage of the compound is 1.1 to 190 weight portions; s2, grinding the first material to obtain the additiveAdding the agent.
Alternatively, the method comprises the steps of: a. mixing Ni2O3Mixing a soluble lithium source and a first solvent to obtain a second material; b. mixing the soluble carbonate with a second solvent to obtain a third material; c. and mixing and reacting the second material and the third material, and taking out a precipitate after reaction to obtain the additive.
The method disclosed by the invention can conveniently and quickly prepare the lithium ion battery anode additive with stable performance, and the anode additive can effectively ensure the cycle stability and the structural stability of the lithium ion battery.
Preferably, in step S1, the Ni is added in an amount of 10 parts by weight2O3The Li2CO3The additive prepared in the proportion range can enable the lithium ion battery to have better cycle stability and structural stability, can also be used as a positive electrode additive for preventing overcharge, and is particularly suitable for being used as the positive electrode additive for preventing overcharge of a lithium iron phosphate battery (with the charge cut-off voltage of 3.8V).
Preferably, in step S1, the Ni is added in an amount of 10 parts by weight2O3The Li2CO3The additive prepared in the proportion range can be used as a positive electrode additive with good lithium supplementing effect and can also be used as a positive electrode additive for preventing overcharge, and is particularly suitable for being used as a positive electrode additive for preventing overcharge of spinel lithium manganate ion batteries and/or nickel cobalt lithium manganate ion (ternary material) batteries (with the cut-off voltage of about 4.35V).
To balance the properties of the prepared positive electrode additive, Ni in step S1 according to the present disclosure2O3May be 50nm to 5 μm, the Li2CO3The average particle diameter of (a) may be 50nm to 20 μm; in step S2, the grinding process is a ball milling process, the time of the ball milling process may be 1-10 hours, and the rotation speed of the ball mill may be 200 and 1000 rpm. Ni in the additive prepared under the above conditions2O3With Li2CO3The particle size of (a) is suitable, so that the additive has good structural stability and chemical properties, and the cycle performance of a lithium ion battery containing the additive disclosed by the invention is further improved. Preferably, the ball milling process in step S2 may be a wet ball milling process, the first material is dispersed in ethanol and then ground, and the slurry obtained after grinding is dried to obtain the additive, where the drying temperature may be 50 to 150 ℃, and the drying time may be 5 to 24 hours.
According to the present disclosure, step c may further include: and taking out the precipitate in the third material, washing the precipitate by using a third solvent, and drying the precipitate to obtain the additive, wherein the drying temperature can be 50-150 ℃ and the drying time can be 1-48 hours, and the obtained additive after washing and drying has a stable structure and low impurity content, so that the positive electrode additive has better chemical properties. The manner of removing the precipitate is not particularly limited and may be a method conventionally employed by those skilled in the art, such as funnel filtration, suction filtration. Preferably, the precipitate is taken out by suction filtration, the precipitate can be washed by the second solvent in the suction filtration process, and the suction filtration conditions can be selected according to actual needs as long as the precipitate can be separated out.
According to the present disclosure, in step a, with respect to 10 parts by weight of Ni2O3The soluble lithium source may be used in an amount of 0.7 to 355 parts by weight, the first solvent may be used in an amount of 7 to 5100 parts by weight, and the Ni may be used in an amount of2O3The average particle diameter of (a) may be 50nm to 5 μm; in step b, with respect to 10 parts by weight of Ni2O3The soluble carbonate may be used in an amount of 1.6 to 355 parts by weight. In this range Ni2O3The dosage proportion of the soluble lithium salt, the first solvent and the soluble carbonate is proper, and the components react fully and completely to prepare the positive electrode additive with excellent performance.
Preferably, in step a, with respect to 10 parts by weight of Ni2O3The soluble lithium source may be used in an amount of 4.3 to 18.7 parts by weight, the first solvent may be used in an amount of 45 to 700 parts by weight,the Ni2O3The average particle diameter of (a) may be 50 to 200 nm; in step b, with respect to 10 parts by weight of Ni2O3The soluble carbonate may be used in an amount of 9.6 to 18.7 parts by weight. The additive prepared under the conditions has a better effect of promoting the improvement of the cycle stability of the lithium ion battery, can be used as a positive electrode additive for preventing overcharge, and is particularly suitable for being used as a positive electrode additive for preventing overcharge of a lithium iron phosphate battery (with the charge cut-off voltage of 3.8V).
Preferably, in step a, with respect to 10 parts by weight of Ni2O3The soluble lithium source may be used in an amount of 15.1 to 355 parts by weight, the first solvent may be used in an amount of 150-5100 parts by weight, and the Ni may be used in an amount of2O3The average particle diameter of (a) may be 50 to 200 nm; in step b, with respect to 10 parts by weight of Ni2O3The soluble carbonate may be used in an amount of 34 to 355 parts by weight.
Further, the mixing manner of the soluble carbonate and the second material in step b is not particularly limited, for example, a manner of dropping the soluble carbonate into the second material by using a dropping funnel device may be adopted, the dropping speed of the soluble carbonate may be 1-2 drops/second, and the dropping funnel may be conventionally adopted by those skilled in the art, for example, a dropping funnel with a capacity of 500mL, and will not be described herein again.
According to the present disclosure, there is no particular limitation on the selection of the first solvent, the second solvent, the soluble lithium source, and the soluble carbonate, for example, the first solvent may be selected from deionized water; the second solvent may be selected from deionized water; the third solvent can be one or more selected from ethanol, methanol, propanol, acetone, diethyl ether and glycol, and is preferably ethanol; the soluble lithium source may be selected from LiCl, LiOH, LiNO3、Li2SO4、Li2C2O4And CH3One or more of COOLi; the soluble carbonate may be selected from K2CO3、Na2CO3And (NH)4)2CO3One or more of them.
A third aspect of the present disclosure provides a positive electrode for a lithium ion battery, including a positive active material, a positive current collector, and the positive electrode additive provided in the first aspect of the present disclosure. Wherein, the positive active material can be selected from LiFePO4/C、LiFe1-aMnaPO4A is more than or equal to 0 and less than or equal to 1), nickel-cobalt-aluminum ternary material, nickel-cobalt-manganese ternary material, lithium manganate, lithium cobaltate and Li3V2(PO4)3And LiVPO4F, and the material of the positive electrode current collector is one or more selected from aluminum, copper and nickel-plated steel. The preparation method of the anode can be that the anode active substance, the anode additive, the conductive agent and the binder are mixed and then evenly coated on the anode current collector, then the anode current collector is placed in a drying box for drying treatment, and finally the anode is prepared after tabletting and rolling cutting.
According to the disclosure, the content of the positive electrode additive may be 0.05-2.5 parts by weight relative to 10 parts by weight of the positive electrode active material, and the content of the positive electrode active material and the positive electrode additive of the positive electrode of the lithium ion battery is within this weight range, so that the lithium ion battery has a high capacity, and the positive electrode of the lithium ion battery has a good structure, thereby ensuring the cycle stability of the lithium ion battery.
A fourth aspect of the present disclosure provides a lithium ion battery including the positive electrode, the negative electrode, and the electrolyte provided by the third aspect of the present disclosure. The negative electrode includes a negative electrode active material and a negative electrode current collector; the negative active material is selected from one or more of natural graphite, artificial graphite, petroleum coke, mesocarbon microbeads, carbon fibers and silicon alloy; the material of the negative electrode current collector is selected from one or more of aluminum, copper, nickel-plated steel and steel, and the electrolyte may be one conventionally used by those skilled in the art, for example, the electrolyte is a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC). The specific form of the lithium ion battery is not limited in the present disclosure, and the lithium ion battery may be a pouch battery, a button battery, or a square battery.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
Ni in examples and comparative examples2O3From Aladdin, Li2CO3Purchased from Aladdin, ethanol from Shenzhen Boleien, LiFePO4The material is prepared from fir by/C, alumium foil by Nanshan Aluminium, Sequoia acetylenica, polyvinylidene fluoride by Abametin, N-methylpyrrolidone by Shenzhen Boleien, lithium metal sheet by fir, artificial graphite by fir, styrene butadiene rubber by New Zealand, sodium carboxymethylcellulose by New Zealand, celgard2400 polypropylene porous membrane by fir, ethylene carbonate and dimethyl carbonate by New Zealand, LiPF6From polyfluoropolo, LiCl from Aladdin, Na2CO3From Aladdin, LiNi1/3Co1/3Mn1/3O2From fir, NiO from alatin.
Example 1
(1) Preparing a positive electrode additive:
s1, mixing 50g of Ni2O3(particle diameter 800nm) and 50g of Li2CO3(particle size of 600nm) to obtain a first material;
s2, placing the first material in a ball mill with the rotating speed of 1000 rpm, adding 200mL of ethanol, mixing and grinding for 1h to obtain ground slurry, and placing the ground slurry in a 60 ℃ oven to dry for 6 h to obtain Ni2O3-Li2CO3The material was mixed, labeled a.
Wherein, based on 100 weight parts of additive A, Li in A2CO3In an amount of 50 parts by weight, Li2CO3Has an average particle diameter of 100nm, Ni2O3Has an average particle diameter of 150 nm.
(2) Preparing the anode of the lithium ion battery:
with LiFePO4the/C is a positive electrode active substance, the A is a positive electrode additive, the aluminum foil is a positive electrode current collector, the acetylene black is a conductive agent, the polyvinylidene fluoride (PVDF) is a binder, the N-methyl pyrrolidone (NMP) is a dispersing agent, and the LiFePO is prepared according to the weight ratio4C: a: acetylene black: PVDF: the weight ratio of NMP is 81.6: 3.4: 10: 5: 50 the components are evenly mixed and then coated on an aluminum foil,and then placing the anode plate in a drying box at 120 ℃ for vacuum drying for 24h, and carrying out tabletting and rolling cutting to obtain the anode plate.
(3) Assembling the lithium ion battery:
uniformly mixing artificial graphite, styrene butadiene rubber, sodium carboxymethylcellulose and water according to a mass ratio of 95:3:2:50, coating on a copper foil, then placing in an oven at 80 ℃ for vacuum drying for 24 hours, tabletting, and rolling and cutting to prepare a negative plate; taking a celgard2400 polypropylene porous membrane as a diaphragm, taking a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1 as electrolyte, and taking LiPF in the electrolyte6The concentration of (3) was 1mol/L, and the positive electrode prepared in (2) was used as a positive electrode. The cell was assembled at room temperature in a glove box filled with argon gas, resulting in cell S1.
Example 2
A battery S2 was produced in the same manner as in example 1, except that the method for producing the positive electrode additive was different, and the method for producing the positive electrode additive of this example included the steps of:
a. 50g of Ni2O3(particle size 50nm), 58g LiCl and 500mL deionized water to obtain a second material, wherein Ni2O3Has an average particle diameter of 50 nm;
b. mixing 144gNa2CO3Dissolving in 500mL of deionized water to obtain a third material;
c. dripping the third material into the second material at a speed of 1 drop/second, mixing and reacting the third material with the second material, performing suction filtration on the third material to take out the precipitate, washing the precipitate for three times by using ethanol, and then performing drying treatment at the temperature of 60 ℃ for 6 hours to obtain Ni2O3-Li2CO3The mixed material, labeled B.
Wherein, based on 100 weight parts of additive B, Li in B2CO3In an amount of 50 parts by weight, Li2CO3Has an average particle diameter of 500nm, Ni2O3Has an average particle diameter of 50 nm.
Example 3
A battery S3 was produced in the same manner as in example 1, except that,
(1) preparing a positive electrode additive:
s1, mixing 20g of Ni2O3(particle diameter: 900nm) and 80g of Li2CO3(particle size 800nm) to obtain a first material;
s2, placing the first material in a ball mill with the rotating speed of 800 revolutions per minute, adding 200mL of ethanol, mixing and grinding for 1.5h to obtain ground slurry, and then placing the obtained slurry in an oven at 60 ℃ to dry for 6 h to obtain Ni2O3-Li2CO3The mixed material, labeled C.
Wherein, based on 100 weight portions of the additive C, Li in the additive C2CO3In an amount of 80 parts by weight, Li2CO3Has an average particle diameter of 200nm, Ni2O3Has an average particle diameter of 200 nm.
(2) Preparing the anode of the lithium ion battery:
with LiNi1/3Co1/3Mn1/3O2Is a positive electrode active material.
Example 4
A battery S4 was produced in the same manner as in example 1, except that,
s1, mixing 70g of Ni2O3(particle diameter of 600nm) and 30g of Li2CO3(particle size 150nm) to obtain a first material;
s2, placing the first material in a ball mill with the rotating speed of 600 revolutions per minute, adding 200mL of ethanol, mixing and grinding for 1.5h to obtain ground slurry, and then placing the obtained slurry in an oven with the temperature of 60 ℃ for drying for 6 h to obtain Ni2O3-Li2CO3The material was mixed, labeled D.
Wherein, based on 100 weight parts of additive D, Li in D2CO3In an amount of 30 parts by weight, Li2CO3Has an average particle diameter of 80nm, Ni2O3Has an average particle diameter of 400 nm.
Example 5
A battery S5 was produced in the same manner as in example 2, except that,
(1) preparing a positive electrode additive:
a. 20g of Ni2O3(particle size 150nm), 93g LiCl and 800mL deionized water to obtain a second material, wherein Ni2O3Has an average particle diameter of 150 nm;
b. adding 210g of Na2CO3Dissolving in 800mL of deionized water to obtain a third material;
c. dripping the third material into the second material at a speed of 2 drops/second, mixing and reacting the third material with the second material, carrying out suction filtration treatment on the mixture to take out the precipitate, washing the precipitate for three times by using ethanol, and then carrying out drying treatment at the temperature of 60 ℃ for 6 hours to obtain Ni2O3-Li2CO3The mixed material, labeled E.
Wherein, based on 100 weight parts of additive E, Li in E2CO3In an amount of 80 parts by weight, Li2CO3Has an average particle diameter of 400nm, Ni2O3Has an average particle diameter of 150 nm.
(2) Preparing the anode of the lithium ion battery:
with LiNi1/3Co1/3Mn1/3O2Is a positive electrode active material.
Example 6
A battery S6 was produced in the same manner as in example 2, except that,
a. 70g of Ni2O3(particle size 100nm), 35g LiCl and 500mL deionized water to obtain a second material, wherein Ni2O3Has an average particle diameter of 50 nm;
b. mixing 86gNa2CO3Dissolving in 500mL of deionized water to obtain a third material;
c. dripping the third material into the second material at a speed of 1 drop/second, mixing and reacting the third material with the second material, performing suction filtration on the third material to take out the precipitate, washing the precipitate for three times by using ethanol, and then performing drying treatment at the temperature of 60 ℃ for 6 hours to obtain Ni2O3-Li2CO3The material was mixed, labeled F.
Wherein, based on 100 weight parts of additive F, Li in F2CO3In an amount of 30 parts by weight, Li2CO3Has an average particle diameter of 300nm, Ni2O3Has an average particle diameter of 100 nm.
Example 7
The battery S7 was produced in the same manner as in example 1, except that LiNi was used in the production of the positive electrode for lithium ion battery in the step (2)1/3Co1/3Mn1/3O2Is a positive electrode active material.
Example 8
A battery S8 was produced in the same manner as in example 1, except that S1 was changed to 40g of Ni2O3(particle diameter 800nm) and 60g of Li2CO3(particle size of 600nm) to obtain a first material;
s2, placing the first material in a ball mill with the rotating speed of 800 revolutions per minute, adding 200mL of ethanol, mixing and grinding for 2 hours to obtain ground slurry, and then placing the obtained slurry in a 60 ℃ oven to dry for 6 hours to obtain Ni2O3-Li2CO3The material was mixed, labeled G.
Wherein, based on 100 weight parts of additive G, Li in G2CO3In an amount of 60 parts by weight, Li2CO3Has an average particle diameter of 100nm, Ni2O3Has an average particle diameter of 150 nm.
Comparative example 1
Battery D1 was prepared in the same manner as in example 1, except that the lithium ion battery of this comparative example did not contain a positive electrode additive and the positive electrode active material was LiFePO4/C。
Comparative example 2
Battery D2 was prepared in the same manner as in example 1, except that the lithium ion battery of this comparative example did not contain a positive electrode additive and the positive electrode active material was LiNi1/3Co1/3Mn1/3O2。
Comparative example 3
By usingCell D3 was prepared in the same manner as in example 5, except that 20g of NiO (particle size 150nm), 93g of LiCl, and 800mL of deionized water were mixed in step a to obtain a second material, in which the average particle size of NiO was 150 nm; b. mixing 210gNa2CO3Dissolved in 800mL of deionized water to obtain a third material.
Wherein, based on 100 weight parts of additive H, Li in H2CO3In an amount of 80 parts by weight, Li2CO3Has an average particle diameter of 400nm and an average particle diameter of NiO of 150 nm.
Comparative example 4
Battery D4 was produced in the same manner as in example 1, except that 93g of Ni was charged in step S12O3(particle diameter 150nm) and 7g of Li2CO3(particle size 150nm) to obtain Ni2O3-Li2CO3The material was mixed, labeled I.
Wherein, based on 100 weight portions of additive I, Li in the additive I2CO3Is contained in an amount of 7 parts by weight, Li2CO3Has an average particle diameter of 30nm, Ni2O3Has an average particle diameter of 30 nm.
Test examples
(1) X-ray diffraction analysis
Ni prepared in example 1 was subjected to Ni-X-ray diffraction using a SmartLab type X-ray diffractometer in Japan2O3-Li2CO3Mixed Material and comparative example 1 NiO-Li preparation2CO3The mixed material was subjected to phase analysis. Analysis conditions were as follows: tube pressure 40kV, tube flow 20mA, Cu ka wire, λ 0.154056nm, using a graphite monochromator, step width 0.02 °, dwell time 0.2s, test results are shown in fig. 1.
(2) Measurement of Charge and discharge Capacity
The lithium ion batteries of examples and comparative examples were subjected to a charge/discharge capacity test on a charge/discharge tester, and it should be noted that the liquid injection hole was not sealed during charging so that the generated gas was discharged, and after the charging was completed, the batteries were sealed and then subjected to a discharge test. The battery is set to a charging state, namely the lithium is removed from the working electrode, the charging current density is 0.1C, the operation is stopped when the battery is charged to the cut-off voltage of 4.4V, and the first charging capacity is read. After the first lithium removal is finished, the battery is set to be in a discharging state, namely the working electrode is embedded with lithium, the discharging current density is 0.1C, discharging is finished when the discharging is finished until the cut-off voltage is 3V, the first discharging capacity is read, and the test result is shown in table 1.
(3) Overcharge resistance test
Carrying out overcharge resistance test on a charge and discharge tester:
(a) the positive electrode active material of the batteries S3, S5, S7 and D2 was LiNi1/3Co1/3Mn1/3O2The battery was charged to 4.3V at 0.1C rate, left to stand for 5min and then charged to 5V at 1C rate, and the state of the battery was observed.
(b) The positive electrode active material of the batteries S1, S2, S4, S6, S8, D1, D3, and D4 was LiFePO4The battery was charged to 3.8V at a rate of 0.1C, left to stand for 5 mm, and then charged to 5V at 1C, and the state of the battery was observed.
Examples 1 to 8 and comparative examples 1 to 4 were divided into two groups for the overcharge resistance test depending on the positive electrode active material of the battery.
The test results are shown in Table 2.
(4) Performance testing of the Positive electrode additive
Lithium ion batteries C1-C8 and DC3-DC4 were prepared in the same procedures (2) and (3) as in example 1, using the positive electrode additive materials prepared in examples 1 to 8 and comparative examples 3 and 4 as positive electrode materials, except that the positive electrode material used in step (2) was the additive material and the negative electrode used in step (3) was a metallic lithium plate. And then carrying out a charge-discharge specific capacity test on a charge-discharge tester, setting the battery to be in a charging state, namely, the lithium is removed from the working electrode, the charging current density is 0.1C, the battery stops running when the battery is charged to a cut-off voltage of 4.5V, and calculating the first charge specific capacity. After the first lithium removal is finished, the battery is set to be in a discharge state, namely the working electrode is embedded with lithium, the discharge current density is 0.1C, the discharge is finished when the discharge is finished until the cut-off voltage is 3V, the first discharge specific capacity is calculated, a charge-discharge curve chart of the batteries C1 and DC3 at the charge-discharge multiplying power of 0.1C is shown in a figure 2, and the test results of the batteries are shown in a table 3.
The first lithium removal specific capacity (mAh/g) is equal to the first lithium removal capacity/the quality of the anode material,
first lithium intercalation specific capacity (mAh/g) ═ first lithium intercalation capacity/mass of the positive electrode material.
(5) Cycle performance test
The lithium ion batteries prepared in examples 1 to 8 and comparative examples 1 to 4 were loaded on a charge and discharge tester, and the batteries S1, S2, S4, S6, S8, D1, D3 and D4 were subjected to 500 cycle performance tests at 25 ℃ under conditions of a current of 0.5C, an upper limit voltage of 3.8V, and a lower limit voltage of 3V; the batteries S3, S5, S7 and D2 were subjected to 500-cycle performance tests at 25 ℃ under the conditions of a current of 0.5C, an upper limit voltage of 4.3V, and a lower limit voltage of 3V. Wherein, the ratio of the 500 th discharge capacity to the 1 st discharge capacity is the normal-temperature cycle capacity retention rate of the battery for 500 times. The test results are shown in table 2. TABLE 1
Battery numbering First charge capacity mAh First discharge capacity mAh
S1 911.6 827.3
S2 910.7 826.8
S3 963.8 886.9
S4 881.2 802.1
S5 962.5 886.1
S6 880.3 801.5
S7 1016.5 915.8
S8 900.2 818.6
D1 868.2 800.8
D2 972.7 895.1
D3 875.1 797.3
D4 869.1 801.0
TABLE 2
Figure BDA0002081297810000161
Figure BDA0002081297810000171
Among them, in the case of overcharge of a lithium ion battery, smoking or ignition and explosion of the lithium ion battery are mainly determined by a positive active material used for the lithium ion battery. When the anode active material is lithium iron phosphate, the lithium removal product is stable at high temperature, and the lithium ion battery cannot be ignited and exploded and only smokes. And when the positive electrode active material is a ternary material (e.g., LiNi)1/3Co1/3Mn1/ 3O2) In the process, the lithium removal product is easy to decompose at high temperature to release oxygen, and the lithium ion battery can be ignited and exploded.
TABLE 3
Figure BDA0002081297810000172
Figure BDA0002081297810000181
The plateau at DC3 was 4.6V, and the cut-off voltage was set at 4.5V, so no plateau was present.
As can be seen from table 1, the lithium ion battery positive electrode additive disclosed by the present disclosure has a good lithium supplementing effect, and can provide a lithium ion battery with good cycle performance and structural stability. Preferably, the Li is added based on 100 parts by weight of the additive2CO3When the content of (a) is 40-50 parts by weight, the positive electrode additive disclosed by the invention can further improve the cycle performance of the lithium ion battery and ensure the structural stability of the positive electrode of the lithium ion battery.
As can be seen from Table 2, the lithium ion battery positive electrode additive disclosed by the invention can be used as a positive electrode safety additive, and the additive is decomposed and started in advance before thermal runaway of the batteryAnd the explosion valve improves the overcharge resistance safety of the battery. Preferably, the Li is added based on 100 parts by weight of the additive2CO3When the content of (b) is 40 to 50 parts by weight, the lithium iron phosphate battery positive electrode additive is particularly suitable for being used as a positive electrode additive for preventing overcharge of a lithium iron phosphate battery (the charge cut-off voltage is 3.8V). Preferably, the Li is added based on 100 parts by weight of the additive2CO3At a concentration of 70-95 parts by weight, the additive of the present disclosure is particularly useful as an overcharge-preventing positive electrode additive for spinel lithium manganate ion batteries and/or lithium nickel cobalt manganate ion (ternary material) batteries (cut-off voltage of about 4.35V).
As can be seen from table 3 and fig. 2, the positive electrode additive of the present disclosure can provide more active lithium to the negative electrode, has a good lithium supplementing effect, and can effectively ensure good cycling stability of the lithium ion battery; simultaneously with NiO-Li2CO3Compared with the additive, when NiO in the additive is compared with Li2CO3The content of the positive electrode additive is the same as that of the two components of the additive, the positive electrode additive has a lower charging voltage platform, and the influence of high charging voltage on the structure of a positive electrode active material can be avoided, so that the stability and the cycle performance of the lithium ion battery are further improved. Preferably, Li is added based on 100 parts by weight of the additive2CO3When the content of (a) is 40-50 parts by weight, the lithium ion battery containing the additive disclosed by the invention has higher initial charge capacity and lower charge voltage platform, and the cycle performance and the structural stability of the lithium ion battery can be further improved.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (11)

1. The additive for the positive electrode of the lithium ion battery is characterized in that the additive is Ni2O3And Li2CO3Wherein the Li is based on 100 parts by weight of the additive2CO3In an amount of 10 to 95 parts by weight, the Li2CO3Has an average particle diameter of 50nm to 20 μm, and Ni2O3Has an average particle diameter of 50nm to 5 μm.
2. Additive according to claim 1, characterized in that the Li is based on 100 parts by weight of the additive2CO3In an amount of 40 to 50 parts by weight, the Li2CO3Has an average particle diameter of 100nm to 500nm, and Ni2O3Has an average particle diameter of 50nm to 200 nm.
3. Additive according to claim 1, characterized in that the Li is present in an amount of 100 parts by weight of the additive2CO3In an amount of 70 to 95 parts by weight, the Li2CO3Has an average particle diameter of 100nm to 500nm, and Ni2O3Has an average particle diameter of 50nm to 200 nm.
4. A process for preparing the additive of any one of claims 1-3, comprising the steps of:
s1, mixing Ni2O3With Li2CO3Mixing to obtain a first material, wherein the Ni is added in an amount of 10 parts by weight2O3The Li2CO3The dosage of the compound is 1.1 to 190 weight portions;
s2, grinding the first material to obtain the additive;
alternatively, the method comprises the steps of:
a. mixing Ni2O3Mixing a soluble lithium source and a first solvent to obtain a second material;
b. mixing the soluble carbonate with a second solvent to obtain a third material;
c. and mixing and reacting the second material and the third material, and taking out a precipitate after reaction to obtain the additive.
5. The method of claim 4, wherein in step S1, Ni2O3Has an average particle diameter of 50nm to 5 μm, and the Li2CO3The average particle diameter of (A) is 50nm-20 μm;
in step S2, the grinding process is a ball milling process, the time of the ball milling process is 1-10 hours, and the rotation speed of the ball mill is 200-.
6. The method of claim 4, wherein step c further comprises: and taking out the precipitate in the third material, washing with a third solvent, and drying to obtain the additive, wherein the drying temperature is 50-150 ℃ and the drying time is 1-48 hours.
7. The method according to claim 4, wherein in the step a, the Ni is added in an amount of 10 parts by weight2O3The soluble lithium source is used in an amount of 0.7 to 355 parts by weight, the first solvent is used in an amount of 7 to 5100 parts by weight, and the Ni is used in an amount of2O3The average particle diameter of (A) is 50nm-5 μm;
in step b, with respect to 10 parts by weight of Ni2O3The soluble carbonate is used in an amount of 1.6 to 355 parts by weight.
8. The method of claim 4 or 6, wherein the first solvent is selected from the group consisting of deionized water; the second solvent is selected from deionized water; the third solvent is selected from ethanol, methanol,One or more of propanol, acetone, diethyl ether and ethylene glycol; the soluble lithium source is selected from LiCl, LiOH, LiNO3、Li2SO4、Li2C2O4And CH3One or more of COOLi; the soluble carbonate is selected from K2CO3、Na2CO3And (NH)4)2CO3One or more of them.
9. A positive electrode for a lithium ion battery, comprising a positive electrode active material, a positive electrode current collector, and the positive electrode additive according to any one of claims 1 to 3.
10. The positive electrode for a lithium ion battery according to claim 9, wherein the positive electrode additive is contained in an amount of 0.05 to 2.5 parts by weight relative to 10 parts by weight of the positive electrode active material.
11. A lithium ion battery comprising the positive electrode according to claim 9 or 10, a negative electrode, and an electrolyte.
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