CN114242939A - Modified positive electrode lithium supplement material and preparation method and application thereof - Google Patents

Modified positive electrode lithium supplement material and preparation method and application thereof Download PDF

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CN114242939A
CN114242939A CN202111563912.6A CN202111563912A CN114242939A CN 114242939 A CN114242939 A CN 114242939A CN 202111563912 A CN202111563912 A CN 202111563912A CN 114242939 A CN114242939 A CN 114242939A
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positive electrode
lithium
lithium supplement
supplement material
modified
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邓孝龙
王忠明
冀亚娟
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Eve Energy Co Ltd
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Eve Energy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention provides a modified anode lithium supplement material and a preparation method and application thereof. The preparation method comprises the following steps: mixing the anode lithium supplement material and the Al source dopant to obtain a mixture; sintering the obtained mixture to obtain a sintered material; and coating the obtained sintering material in a carbon source gas atmosphere to obtain the modified anode lithium supplement material. According to the invention, surface phase doping is carried out through Al, so that the structural stability and the thermal stability of the material are improved, meanwhile, the corrosion of HF in the electrolyte to the active material is prevented, the surface impedance is reduced, and the cycle performance is improved. Through carrying out carbon nano-layer cladding to anodal lithium material not only isolated the contact of active material with electrolyte, effectively reduced the emergence of side reaction, simultaneously, promoted the storage stability and the processing property of material, the effectual electric conductive property that has promoted anodal lithium material of mending.

Description

Modified positive electrode lithium supplement material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a modified anode lithium supplement material, and particularly relates to a modified anode lithium supplement material as well as a preparation method and application thereof.
Background
With the rapid development of consumer electronics and electric automobile industries, higher requirements are put on the performance and safety of new batteries, and the requirement that the batteries can endure various extreme operating conditions is increasing. In order to achieve longer standby time and longer driving range, people continuously pursue a method for further improving the energy density of the battery, and work is mainly carried out from the following two aspects: (1) developing battery systems with higher energy density, such as lithium-sulfur batteries, lithium air batteries, and the like; (2) improvements are made over existing commercial lithium ion battery systems. However, all the brand new high energy density lithium ion battery systems have the problems of fast capacity attenuation, dendritic crystal growth of a lithium metal negative electrode and the like, and the problems cannot be solved properly in a short time, so that the application of the lithium ion battery systems is greatly restricted.
The positive electrode material and the negative electrode material of the existing commercial lithium ion battery have a large irreversible capacity loss in the first week, the positive electrode material is mainly due to collapse of the material structure after lithium removal, the positions of lithium ions which can be accommodated are reduced, and the first coulombic efficiency is low, while the application of the negative electrode material, especially a novel negative electrode material (such as silicon or tin), although the capacity is greatly improved, the irreversible capacity is up to more than 30%, and the battery capacity is remarkably reduced. In order to solve the problem of the first irreversible capacity loss, researchers develop a lithium supplement technology, and a new lithium source is added in an electrode material in a lithium supplement mode to compensate the loss of active lithium caused by the SEI film formed in the first cycle. The negative electrode lithium supplement material is extremely unstable in air, is very difficult to store and transport, and the negative electrode lithium supplement process has extremely strict requirements on the environmental humidity, is expensive in cost and is easy to generate lithium dendrites to influence the safety performance.
In recent years, the positive electrode lithium supplement has gradually received from people due to the advantages of relative stability, easy synthesis, low price, high lithium supplement capability and the likeTo focus on. Wherein Li2NiO2The lithium ion battery anode material is a typical lithium-rich compound anode lithium supplement additive, can release lithium ions at more than 3.5V, has the first-week theoretical charge capacity higher than 480mAh/g, can greatly improve the energy density of a lithium ion battery when being used as the anode material lithium supplement additive, but has high residual lithium content on the surface, difficult processing and poor surface stability, is easy to generate gas by side reaction with electrolyte in the long-term charge and discharge process, and is easy to pierce a diaphragm to cause the risk of short circuit because metal ions are dissolved out from the cathode.
CN 113140722A discloses a positive electrode lithium supplement material, a preparation method and an application thereof, wherein the positive electrode lithium supplement material comprises Li2-xNi1-yMyO2And coating with Li2-xNi1-yMyO2Superficial MemOnA coating layer; the invention adopts low-cost metal elements to carry out precursor coprecipitation doping, and replaces part of Ni while reducing the cost2+The mixed lithium-nickel discharging is reduced, the structure is stabilized in the cell circulation process, the oxygen release amount is reduced, and the lithium-nickel mixed discharging in Li2-xNi1-yMyO2Surface coating MemOnThe coating layer greatly reduces the residual lithium content of the finished product, improves the processing and gas production performance, and can inhibit the dissolution deposition anode of transition metals of nickel, copper and iron from damaging an SEI film, thereby improving the cycle.
CN 112397766a discloses a high-voltage physical ion battery and a preparation method thereof, wherein the positive electrode comprises a positive active material, and the positive active material comprises two compounds; wherein the chemical formula of the compound 1 is LixCo1-yMey02；0.95≤x≤1.05，0≤y≤0.1；Me＝(Mz1Nz2) 0. ltoreq. z 1. ltoreq.1, 0. ltoreq. z 2. ltoreq.1, M and N are identical or different and are selected, independently of one another, from Al, Mg, Ti, Zr, Co, Ni, Mn, Y, La, Sr: the chemical formula of the compound 2 is Li2Ni1-aDaO2(ii) a A is more than or equal to 0 and less than or equal to 0.1; d is selected from Al,At least one of Mg, Ti, Zn, Fe, Co, Mn: through a high-voltage diamond acid physical chemical compound with stable structure and Li with doping coating2NiO2The compounds are mixed according to a certain proportion, and are applied to a high-voltage physical ion battery system, the first efficiency of the graphite material and silicon material blended negative electrode is obviously improved, the physical ion battery formed by combining the materials can obviously improve the volume energy density, and meanwhile, the cycle performance of the physical ion battery material is improved.
Li additive for lithium in the above technical scheme2NiO2The structure and the composition of the modified lithium-supplementing material are improved, but the preparation process of the modified lithium-supplementing material in CN 113140722A is complex, the addition of coated metal ions is complex, and the conductivity is still poor; the lithium supplement agent in CN 112397766A can not isolate the contact of the active material and the electrolyte, thereby reducing the occurrence of side reaction and reducing the gas generation and the dissolution of metal ions in the negative electrode.
How to overcome Li2NiO2The material has high surface residual lithium content and difficult processing, can solve the problems that the material is easy to generate side reaction with electrolyte to generate gas, and is easy to dissolve out of a negative electrode and poor in conductivity, and is a technical problem to be solved in the technical field of lithium ion batteries.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a modified anode lithium supplement material and a preparation method and application thereof, the anode lithium supplement material is subjected to surface phase doping by Al, the structural stability and the thermal stability of the material are improved, meanwhile, the corrosion of HF in electrolyte to an active material is prevented, the surface impedance is reduced, the cycle performance is improved, the contact between the active material and the electrolyte is isolated through carbon nano-layer coating, the occurrence of side reactions is effectively reduced, the gas generation and the dissolution of metal ions in a negative electrode are reduced, meanwhile, the specific surface area of the material can be effectively reduced through the coating of a nano carbon layer, residual lithium on the surface of the material is coated, and the storage stability and the processing performance of the material are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a modified cathode lithium supplement material, which comprises the following steps:
(1) mixing the anode lithium supplement material and the Al source dopant to obtain a mixture;
(2) sintering the mixture obtained in the step (1) to obtain a sintered material;
(3) and (3) coating the sintered material obtained in the step (2) in a carbon source gas atmosphere to obtain the modified anode lithium supplement material.
According to the invention, Al is adopted for surface doping, so that on one hand, Al can be doped into tetrahedral vacancies of a crystal structure on the surface layer of particles, and the material is inhibited from being transformed to a rock salt phase; on the other hand, Al ions can react with residual alkali on the surface of the anode lithium supplement material, so that the content of the residual alkali is reduced; meanwhile, the Al-O bond energy is higher, so that the corrosion of HF in the electrolyte to the active material can be resisted, the surface impedance is reduced, and the cycle performance is improved.
Preferably, the positive electrode lithium supplement material in the step (1) comprises Li2NiO2。
Preferably, the Al source dopant of step (1) comprises any one of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum fluoride or aluminum phosphate or a combination of at least two thereof. Typical but non-limiting combinations include combinations of aluminum hydroxide and aluminum oxide, combinations of aluminum oxide and aluminum chloride, combinations of aluminum chloride and aluminum fluoride, combinations of aluminum fluoride and aluminum phosphate, combinations of aluminum hydroxide, aluminum oxide and aluminum chloride, combinations of aluminum oxide, aluminum chloride, aluminum fluoride and aluminum phosphate, combinations of aluminum oxide, aluminum chloride and aluminum fluoride, combinations of aluminum hydroxide, aluminum oxide, aluminum chloride and aluminum fluoride.
Preferably, the Al-source dopant of step (1) has a particle size in the range of 0.02-2 μm, such as 0.02 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, or 2 μm, but is not limited to the recited values, and other values in the range of values not recited are equally applicable.
Preferably, the mass of Al in the mixture in step (1) is 0.1-0.3 wt% of the positive electrode lithium supplement material, for example, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt% or 0.3 wt%, but not limited to the recited values, and other values in the range are also applicable.
Preferably, the mixing of step (1) is performed under an air atmosphere, a nitrogen atmosphere, or an inert gas atmosphere.
Preferably, the air atmosphere has a dew point of ≦ -40 deg.C, such as-40 deg.C, -50 deg.C, -60 deg.C, -70 deg.C, or-80 deg.C, but is not limited to the recited values, and other values in the range of values are equally applicable.
The mixing in the air atmosphere provided by the invention is carried out in the dry air atmosphere, and the dry air atmosphere needs to meet the requirement that the dew point is less than or equal to-40 ℃.
Preferably, the sintering temperature in step (2) is 400-700 ℃, for example 400 ℃, 500 ℃, 550 ℃, 600 ℃ or 700 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the sintering time in step (2) is 4-20h, such as 4h, 8h, 10h, 15h or 20h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the carbon source gas of step (3) comprises any one or a combination of at least two of acetylene, ethylene, methane or ethane, typical but non-limiting combinations include a combination of acetylene and ethylene, a combination of ethylene and methane, a combination of methane and ethane, a combination of acetylene and methane, a combination of acetylene, ethylene and methane, a combination of ethylene, methane and ethane, or a combination of acetylene, ethylene, methane and ethane,
preferably, the temperature of the coating in step (3) is 650- & 800 ℃, for example 650 ℃, 700 ℃, 750 ℃, 780 ℃ or 800 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the coating time in step (3) is 0.5-5h, such as 0.5h, 1h, 2h, 3h, 4h or 5h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferable technical solution of the preparation method of the first aspect of the present invention, the preparation method comprises the steps of:
(1) mixing the positive electrode lithium-supplementing material Li in air atmosphere, nitrogen atmosphere or inert gas atmosphere2NiO2Mixing with Al source dopant to obtain mixture; the mass of the Al is 0.1-0.3 wt% of that of the positive electrode lithium supplement material;
(2) sintering the mixture obtained in the step (1) at the temperature of 400-;
(3) coating the sintering material obtained in the step (2) in a carbon source gas atmosphere, wherein the coating temperature is 650-800 ℃, and the coating time is 0.5-5h, so as to obtain the modified anode lithium supplement material;
the Al source dopant comprises any one of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum fluoride or aluminum phosphate or a combination of at least two of the aluminum hydroxide, the aluminum oxide, the aluminum chloride, the aluminum fluoride or the aluminum phosphate; the grain diameter is 0.02-2 μm;
the carbon source gas comprises any one of acetylene, ethylene, methane or ethane or a combination of at least two of the foregoing.
In a second aspect, the invention provides a modified cathode lithium supplement material, which is obtained by the preparation method of the first aspect.
In a third aspect, the invention provides a lithium ion battery positive plate, which contains the modified positive electrode lithium supplement material according to the second aspect.
Preferably, the mass of the modified positive electrode lithium supplement material is 0.1-10 wt% of the lithium ion battery positive electrode sheet, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
The modified anode lithium supplement material provided by the invention is suitable for a battery system with an anode active substance of any one or at least two of ternary materials, binary materials, lithium nickelate, lithium cobaltate, lithium iron phosphate or lithium manganate.
In a fourth aspect, the invention provides a lithium ion battery, wherein the modified positive electrode lithium supplement material according to the second aspect is contained in the lithium ion battery.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, surface phase doping is carried out through Al, so that the structural stability and the thermal stability of the material are improved, meanwhile, the corrosion of HF in the electrolyte to the active material is prevented, the surface impedance is reduced, and the cycle performance is improved.
(2) According to the invention, the carbon nano-layer coating is carried out on the positive electrode lithium supplement material, so that the contact between the active material and the electrolyte is isolated, the occurrence of side reactions is effectively reduced, the storage stability and the processing performance of the material are improved, and the conductivity of the positive electrode lithium supplement material is effectively improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a lithium ion battery positive plate, which contains a modified positive electrode lithium supplement material with the mass percentage of 5 wt%, and further comprises a positive electrode active substance (lithium cobaltate), a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nano tubes in the mass ratio of 1: 1), wherein the mass ratio of the positive electrode active substance to the binder to the conductive agent is 92:1: 2.
The preparation method of the modified anode lithium supplement material comprises the following steps:
(1) mixing Li in an air atmosphere with a dew point of-40 DEG C2NiO2Mixing with alumina to obtain a mixture; the mass of the alumina is Li2NiO20.2 wt% of;
(2) sintering the mixture obtained in the step (1) at the temperature of 500 ℃ for 10h to obtain a sintered material;
(3) and (3) coating the sintered material obtained in the step (2) in a methane gas atmosphere, wherein the coating temperature is 720 ℃, and the coating time is 2.5h, so as to obtain the modified anode lithium supplement material.
Example 2
The embodiment provides a lithium ion battery positive plate, which contains a modified positive lithium supplement material with a mass percentage of 4.5 wt%, and further comprises a positive active material (lithium cobaltate), a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nanotubes in a mass ratio of 1: 1), wherein the mass ratio of the positive active material to the binder to the conductive agent is 92:1.5: 2.
The preparation method of the modified anode lithium supplement material comprises the following steps:
(1) mixing Li under nitrogen atmosphere2NiO2Mixing with aluminum chloride to obtain a mixture; the mass of the aluminum chloride is Li2NiO20.15 wt% of;
(2) sintering the mixture obtained in the step (1) at the temperature of 450 ℃ for 15h to obtain a sintered material;
(3) and (3) coating the sintered material obtained in the step (2) in an ethylene gas atmosphere, wherein the coating temperature is 700 ℃, and the coating time is 4 hours, so as to obtain the modified anode lithium supplement material.
Example 3
The embodiment provides a lithium ion battery positive plate, which contains a modified positive electrode lithium supplement material with the mass percentage of 5.5 wt%, and further comprises a positive electrode active substance (lithium cobaltate), a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nano tubes in the mass ratio of 1: 1), wherein the mass ratio of the positive electrode active substance to the binder to the conductive agent is 92:0.5: 2.
The preparation method of the modified anode lithium supplement material comprises the following steps:
(1) mixing Li under argon atmosphere2NiO2And aluminum fluoride to obtain a mixture; the mass of the aluminum fluoride is Li2NiO20.25 wt% of;
(2) sintering the mixture obtained in the step (1) at the temperature of 600 ℃ for 7h to obtain a sintered material;
(3) and (3) coating the sintered material obtained in the step (2) in an ethane gas atmosphere, wherein the coating temperature is 760 ℃, and the coating time is 1h, so as to obtain the modified anode lithium supplement material.
Example 4
The embodiment provides a lithium ion battery positive plate, which contains a modified positive electrode lithium supplement material with the mass percentage of 5 wt%, and further comprises a positive electrode active substance (lithium cobaltate), a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nano tubes in the mass ratio of 1: 1), wherein the mass ratio of the positive electrode active substance to the binder to the conductive agent is 92:1: 2.
The preparation method of the modified anode lithium supplement material comprises the following steps:
(1) mixing Li under helium atmosphere2NiO2Mixing with aluminum hydroxide to obtain a mixture; the mass of the aluminum hydroxide is Li2NiO20.1 wt% of;
(2) sintering the mixture obtained in the step (1) at the temperature of 400 ℃ for 20 hours to obtain a sintered material;
(3) and (3) coating the sintered material obtained in the step (2) in an acetylene gas atmosphere, wherein the coating temperature is 650 ℃, and the coating time is 5 hours, so as to obtain the modified anode lithium supplement material.
Example 5
The embodiment provides a lithium ion battery positive plate, which contains a modified positive electrode lithium supplement material with the mass percentage of 5 wt%, and further comprises a positive electrode active substance (lithium cobaltate), a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nano tubes in the mass ratio of 1: 1), wherein the mass ratio of the positive electrode active substance to the binder to the conductive agent is 92:1: 2.
The preparation method of the modified anode lithium supplement material comprises the following steps:
(1) mixing Li in an air atmosphere with a dew point of-50 DEG C2NiO2Mixing with aluminum phosphate to obtain a mixture; the aluminum phosphate is Li by mass2NiO20.3 wt% of;
(2) sintering the mixture obtained in the step (1) at 700 ℃ for 4h to obtain a sintered material;
(3) and (3) coating the sintered material obtained in the step (2) in an acetylene gas atmosphere, wherein the coating temperature is 800 ℃, and the coating time is 0.5h, so as to obtain the modified anode lithium supplement material.
Example 6
The embodiment provides a lithium ion battery positive plate, and the preparation method of the modified positive electrode lithium supplement material comprises the step (1) of preparing the lithium ion battery positive plate by using the aluminum oxide as the positive electrode lithium supplement material Li2NiO2Except for 0.05 wt%, the remaining components and process steps were the same as in example 1.
Example 7
The embodiment provides a lithium ion battery positive plate, and the preparation method of the modified positive electrode lithium supplement material comprises the step (1) of preparing the lithium ion battery positive plate by using the aluminum oxide as the positive electrode lithium supplement material Li2NiO2Other than 0.35 wt%, the remaining components and process steps were the same as in example 1.
Example 8
The embodiment provides a lithium ion battery positive plate, and the components and process steps are the same as those in embodiment 1 except that methane gas is replaced by ethylene gas in step (3) in the preparation method of the modified positive electrode lithium supplement material.
Example 9
The embodiment provides a lithium ion battery positive plate, and the components and process steps are the same as those in embodiment 1 except that in the preparation method of the modified positive lithium supplement material, the methane gas in step (3) is replaced by acetylene gas.
Example 10
The embodiment provides a lithium ion battery positive plate, and the components and process steps are the same as those in embodiment 1 except that methane gas is replaced by ethane gas in step (3) in the preparation method of the modified positive electrode lithium supplement material.
Example 11
The embodiment provides a lithium ion battery positive plate, which contains a modified positive electrode lithium supplement material with the mass percentage of 7.5 wt%, and further comprises a positive electrode active substance (lithium iron phosphate), a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nano tubes in a mass ratio of 4: 3), wherein the mass ratio of the positive electrode active substance to the binder to the conductive agent is 89:1.5: 2.
The preparation method of the modified positive electrode lithium supplement material is the same as that of the embodiment 1.
Example 12
The embodiment provides a lithium ion battery positive plate, which contains a modified positive electrode lithium supplement material with the mass percentage of 1.5 wt%, and further comprises a positive electrode active material (LiNi)0.83Co0.11Mn0.06O2) The positive electrode comprises a positive electrode active material, a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nanotubes in a mass ratio of 1: 1), wherein the mass ratio of the positive electrode active material to the binder to the conductive agent is 95.5:1.5: 1.5.
The preparation method of the modified positive electrode lithium supplement material is the same as that of the embodiment 1.
Example 13
The embodiment provides a lithium ion battery positive plate, which contains a modified positive electrode lithium supplement material with a mass percentage of 4.0%, and further comprises a positive electrode active substance (lithium manganate), a binder (polyvinylidene fluoride) and a conductive agent (carbon black and carbon nanotubes in a mass ratio of 2: 1), wherein the mass ratio of the positive electrode active substance to the binder to the conductive agent is 93.5:1.3: 1.2.
The preparation method of the modified positive electrode lithium supplement material is the same as that of the embodiment 1.
Comparative example 1
The comparative example provides a lithium ion battery positive plate, and the components and process steps are the same as those in example 1 except that the alumina in the step (1) in the preparation method of the modified positive lithium supplement material is replaced by titanium oxide with equal mass.
Comparative example 2
The comparative example provides a lithium ion battery positive plate, and the components and process steps are the same as those in example 1 except that the alumina in the step (1) in the preparation method of the modified positive electrode lithium supplement material is replaced by zirconia with equal mass.
Comparative example 3
The comparative example provides a lithium ion battery positive plate, and the components and process steps are the same as those in example 1 except that the alumina in the step (1) in the preparation method of the modified positive electrode lithium supplement material is replaced by the boron oxide with the same mass.
Comparative example 4
The comparative example provides a lithium ion battery positive plate, which comprises a positive active material, a binder, a conductive agent and a modified positive lithium supplement material, wherein the mass ratio of the positive active material to the binder to the conductive agent to the modified positive lithium supplement material is 92:1:2:5, and the compositions of the positive active material, the binder and the conductive agent are the same as those of the embodiment 1.
The preparation method of the carbon-coated anode lithium supplement material comprises the following steps:
(1) sintering the mixture obtained in the step (1) at the temperature of 500 ℃ for 10h to obtain a sintered material;
(2) and (3) coating the sintered material obtained in the step (2) in a methane gas atmosphere, wherein the coating temperature is 720 ℃, and the coating time is 2.5h, so as to obtain the carbon-coated anode lithium supplement material.
Comparative example 5
The comparative example provides a lithium ion battery positive plate, which comprises a positive active material, a binder, a conductive agent and a modified positive lithium supplement material, wherein the mass ratio of the positive active material to the binder to the conductive agent to the modified positive lithium supplement material is 92:1:2:5, and the compositions of the positive active material, the binder and the conductive agent are the same as those of the embodiment 1.
The preparation method of the aluminum-doped anode lithium supplement material comprises the following steps:
(1) mixing Li in an air atmosphere with a dew point of-40 DEG C2NiO2Mixing with alumina to obtain a mixture; the mass of the alumina is Li2NiO20.2 wt% of;
(2) and (3) sintering the mixture obtained in the step (1) at the temperature of 500 ℃ for 10h to obtain the aluminum-doped positive electrode lithium supplement material.
Comparative example 6
This comparative example provides a lithium ion battery positive plate except that lithium ion batteryThe modified anode lithium supplement material in the anode plate is replaced by the Li with the same quality and unaptimized modification2NiO2Except that, the contents of the remaining components were the same as in example 11.
Comparative example 7
The comparative example provides a lithium ion battery positive plate, except that the modified positive electrode lithium-supplementing material in the lithium ion battery positive plate is replaced by the Li with the same quality and the non-optimized modification2NiO2Except that, the contents of the remaining components were the same as in example 12.
Comparative example 8
The comparative example provides a lithium ion battery positive plate, except that the modified positive electrode lithium-supplementing material in the lithium ion battery positive plate is replaced by the Li with the same quality and the non-optimized modification2NiO2Except that, the contents of the remaining components were the same as in example 13.
The lithium ion battery positive plates obtained in the embodiments 1 to 16 and the comparative examples 1 to 8 and the negative electrode plate are assembled to obtain a soft package battery cell of model 396389, the volume expansion rate of the soft package battery cell in high-temperature storage at 60 ℃/7 days, the capacity retention rate at 3C multiplying power, the capacity retention rate at-20 ℃ and the high-temperature cycle retention rate at 45 ℃ are tested, and the test structure is shown in Table 1.
TABLE 1
Figure BDA0003421170670000131
Figure BDA0003421170670000141
From the data in table 1, the following conclusions can be drawn:
(1) from examples 1 to 5, it can be seen that the modified cathode lithium supplement material provided by the invention improves the structural stability and thermal stability of the material, improves the cycle performance and improves the conductivity of the material by surface phase Al doping and carbon coating, and the prepared lithium ion battery cathode sheet has high cycle stability, good low temperature and rate capability, and can effectively inhibit gas generation in the charging and discharging process.
(2) It can be known from the comparison between examples 6 and 7 and example 1 that, when the content of the surface phase Al doping is greater than 0.3 wt% of the positive electrode lithium supplement material or less than 0.1 wt% of the positive electrode lithium supplement material, the prepared lithium ion battery positive plate has high volume expansion rate, low capacity retention rate under high rate, low temperature capacity retention rate and low high temperature cycle retention rate, which indicates that the content of the surface phase Al ion doping provided by the invention is beneficial to preparing the lithium ion battery positive plate which has good high temperature cycle stability, good low temperature and rate performance and can effectively inhibit the gas production in the charging and discharging process.
(3) From the comparison between the examples 8 to 10 and the example 1, it can be known that the carbon source gas of acetylene, ethylene, methane or ethane provided by the invention realizes carbon coating of the positive electrode lithium supplement material by a chemical vapor deposition method, so that the cycle performance is improved, the conductivity of the material is improved, and the prepared positive plate of the lithium ion battery has high cycle stability, good low temperature and rate capability, and can effectively inhibit gas generation in the charging and discharging process.
(4) As can be seen from comparison of comparative examples 1-3 with example 1, when Ti, Zr or B replaces Al to perform surface phase doping, the prepared lithium ion battery positive plate has high volume expansion rate, low capacity retention rate under high rate, low temperature capacity retention rate and low high temperature cycle retention rate, which indicates that the surface phase Al ion doping provided by the invention is beneficial to preparing the lithium ion battery positive plate which has good high temperature cycle stability, good low temperature and rate performance and can effectively inhibit gas generation in the charging and discharging process.
(5) Compared with the comparative example 4 and the example 1, the comparison shows that when the surface phase doping is not carried out, the prepared lithium ion battery positive plate has high volume expansion rate, low capacity retention rate under high rate, low temperature capacity retention rate and low high temperature cycle retention rate, which shows that the surface phase Al doping provided by the invention is beneficial to preparing the lithium ion battery positive plate which has high cycle stability, good low temperature and rate performance and can effectively inhibit the gas generation in the charging and discharging process.
(6) It can be known from comparison of comparative example 5 and example 1 that, when carbon coating is not performed, the prepared lithium ion battery positive plate has high volume expansion rate, low capacity retention rate under high rate, low temperature capacity retention rate and low high temperature cycle retention rate, which indicates that the carbon coating provided by the invention is beneficial to preparing the lithium ion battery positive plate which has high temperature cycle stability, good low temperature and rate performance and can effectively inhibit gas generation in the charging and discharging process.
(7) As can be seen from the comparison between example 11 and comparative example 6, between example 12 and comparative example 7, and between example 13 and comparative example 8, the modified positive electrode lithium supplement material provided by the present invention is widely applicable to a battery system of a ternary material, a binary material, lithium cobaltate or lithium iron phosphate as a positive electrode active material.
In conclusion, the modified positive electrode lithium supplement material provided by the invention improves the structural stability and the thermal stability of the material, improves the cycle performance and the conductivity of the material through surface phase Al doping and carbon coating, and the prepared positive electrode plate of the lithium ion battery has high cycle stability, good low temperature and rate capability and can effectively inhibit gas generation in the charging and discharging process.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the modified positive electrode lithium supplement material is characterized by comprising the following steps:
(1) mixing the anode lithium supplement material and the Al source dopant to obtain a mixture;
(2) sintering the mixture obtained in the step (1) to obtain a sintered material;
(3) and (3) coating the sintered material obtained in the step (2) in a carbon source gas atmosphere to obtain the modified anode lithium supplement material.
2. Preparation according to claim 1The method is characterized in that the positive electrode lithium supplement material in the step (1) comprises Li2NiO2；
Preferably, the Al source dopant of step (1) comprises any one of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum fluoride or aluminum phosphate or a combination of at least two thereof;
preferably, the particle size of the Al-source dopant of step (1) is in the range of 0.02 to 2 μm;
preferably, the mass of Al in the mixture in the step (1) is 0.1-0.3 wt% of the positive electrode lithium supplement material.
3. The production method according to claim 1 or 2, wherein the mixing of step (1) is performed under an air atmosphere, a nitrogen atmosphere, or an inert gas atmosphere;
preferably, the dew point of the air atmosphere is ≦ 40 ℃.
4. The method as claimed in any one of claims 1 to 3, wherein the sintering temperature in step (2) is 400-700 ℃;
preferably, the sintering time in the step (2) is 4-20 h.
5. The production method according to any one of claims 1 to 4, wherein the carbon source gas of step (3) comprises any one of acetylene, ethylene, methane or ethane or a combination of at least two thereof;
preferably, the temperature of the coating in the step (3) is 650-800 ℃;
preferably, the coating time in the step (3) is 0.5-5 h.
6. The production method according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) mixing the positive electrode lithium-supplementing material Li in air atmosphere, nitrogen atmosphere or inert gas atmosphere2NiO2Mixing with Al source dopant to obtain mixture; the mass of the Al is 0.1-0.3 wt% of that of the positive electrode lithium supplement material;
(2) sintering the mixture obtained in the step (1) at the temperature of 400-;
(3) coating the sintering material obtained in the step (2) in a carbon source gas atmosphere, wherein the coating temperature is 650-800 ℃, and the coating time is 0.5-5h, so as to obtain the modified anode lithium supplement material;
the Al source dopant comprises any one of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum fluoride or aluminum phosphate or a combination of at least two of the aluminum hydroxide, the aluminum oxide, the aluminum chloride, the aluminum fluoride or the aluminum phosphate; the grain diameter is 0.02-2 μm;
the carbon source gas comprises any one of acetylene, ethylene, methane or ethane or a combination of at least two of the foregoing.
7. A modified positive electrode lithium supplement material, which is obtained by the preparation method of any one of claims 1 to 6.
8. A positive plate of a lithium ion battery, characterized in that the modified positive electrode lithium supplement material of claim 7 is contained in the positive plate of the lithium ion battery.
9. The positive plate of the lithium ion battery according to claim 8, wherein the mass of the modified positive electrode lithium supplement material is 0.1-10 wt% of the positive plate of the lithium ion battery.
10. A lithium ion battery, characterized in that the modified positive electrode lithium supplement material according to claim 7 is contained in the lithium ion battery.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114709391A (en) * 2022-04-01 2022-07-05 湖北亿纬动力有限公司 Positive electrode lithium supplement material, preparation method thereof and lithium ion battery
CN115312773A (en) * 2022-05-31 2022-11-08 深圳市德方创域新能源科技有限公司 Doped lithium supplement additive and preparation method and application thereof
CN115557543A (en) * 2022-10-17 2023-01-03 国联汽车动力电池研究院有限责任公司 Surface in-situ coated type positive electrode lithium supplement material and preparation method thereof
CN115566173A (en) * 2022-10-24 2023-01-03 无锡零一未来新材料技术研究院有限公司 Lithium supplement additive and preparation method and application thereof
WO2023216100A1 (en) * 2022-05-10 2023-11-16 宁德时代新能源科技股份有限公司 Battery pack and electric device
WO2024012441A1 (en) * 2022-07-12 2024-01-18 深圳市德方创域新能源科技有限公司 Lithium supplementing additive for positive electrode, and preparation method therefor and use thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114709391A (en) * 2022-04-01 2022-07-05 湖北亿纬动力有限公司 Positive electrode lithium supplement material, preparation method thereof and lithium ion battery
WO2023216100A1 (en) * 2022-05-10 2023-11-16 宁德时代新能源科技股份有限公司 Battery pack and electric device
CN115312773A (en) * 2022-05-31 2022-11-08 深圳市德方创域新能源科技有限公司 Doped lithium supplement additive and preparation method and application thereof
WO2024012441A1 (en) * 2022-07-12 2024-01-18 深圳市德方创域新能源科技有限公司 Lithium supplementing additive for positive electrode, and preparation method therefor and use thereof
CN115557543A (en) * 2022-10-17 2023-01-03 国联汽车动力电池研究院有限责任公司 Surface in-situ coated type positive electrode lithium supplement material and preparation method thereof
CN115557543B (en) * 2022-10-17 2024-01-02 国联汽车动力电池研究院有限责任公司 Surface in-situ coating type positive electrode lithium supplementing material and preparation method thereof
CN115566173A (en) * 2022-10-24 2023-01-03 无锡零一未来新材料技术研究院有限公司 Lithium supplement additive and preparation method and application thereof
CN115566173B (en) * 2022-10-24 2024-04-09 无锡零一未来新材料技术研究院有限公司 Lithium supplementing additive and preparation method and application thereof

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