CN113745460A - Positive pole piece of high-energy-density lithium ion battery and preparation method and application thereof - Google Patents

Positive pole piece of high-energy-density lithium ion battery and preparation method and application thereof Download PDF

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CN113745460A
CN113745460A CN202111014869.8A CN202111014869A CN113745460A CN 113745460 A CN113745460 A CN 113745460A CN 202111014869 A CN202111014869 A CN 202111014869A CN 113745460 A CN113745460 A CN 113745460A
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mixing
positive electrode
lithium
pole piece
positive pole
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CN113745460B (en
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莫方杰
李�昊
李若楠
孙化雨
其他发明人请求不公开姓名
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai 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
    • H01M4/13—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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
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    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
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    • 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
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    • 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
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    • 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
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    • 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
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Abstract

The invention relates to a positive pole piece of a high-energy-density lithium ion battery and a preparation method and application thereof. The positive electrodeThe raw materials of the sheet comprise a lithium supplement material and a positive electrode material, wherein the lithium supplement material is MOzWith Li5FeO4Mixture of (A), the MOzIncluding Al2O3、MgO、SiO2Or a combination of at least two of the transition metal oxides. The lithium supplement material and the anode material are mixed to prepare the composite electrode plate, and the strong bond energy of metal M and metal O in the lithium supplement material inhibits the separation of oxygen elements, so that the oxidative gas production of the battery is inhibited, the gas production of the battery in the storage process is reduced, and the overall stability of the battery is improved.

Description

Positive pole piece of high-energy-density lithium ion battery and preparation method and application thereof
Technical Field
The invention relates to the field of lithium ion batteries, and relates to a positive pole piece, a preparation method and application thereof, in particular to a positive pole piece of a high-energy-density lithium ion battery, and a preparation method and application thereof.
Background
The most direct method for increasing the energy density of lithium ion batteries is to use a high specific capacity positive electrode material. Positive electrode ternary layered material (LiNi)xCoyMn1-x-yO2) The first coulombic efficiency of (a) is 88%, and the positive electrode lithium iron phosphate (LiFePO)4) The first coulombic efficiency of (a) is 98%. Lithium ion supplement material Li widely studied at present5FeO4(LFO) has higher first charge capacity (> 700mAh/g) and lower first coulombic efficiency (< 10%) with good lithium ion replenishment effect. However, in the LFO material, the oxidation energy level of part of lattice oxygen is around 4.2V for lithium potential, and therefore, oxygen is released during the first charge. The released oxygen reacts with the electrolyte to destroy a stable CEI film between the positive electrode and the electrolyte, thereby deteriorating the stability of the battery and even causing a safety problem.
How to effectively improve the energy density of the lithium ion battery and the stability of the battery in the storage cycle is an important research direction in the field of the lithium ion battery anode material.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a positive pole piece of a high-energy-density lithium ion battery, and a preparation method and application thereof.
In order to achieve the technical effects, the invention adopts the following technical scheme:
one of the objectives of the present invention is to provide a positive electrode plate of a high energy density lithium ion battery, wherein the positive electrode plate comprises a lithium supplement material and a positive electrode material, and the lithium supplement material is MOzWith Li5FeO4Mixture of (A), the MOzIncluding Al2O3、MgO、SiO2Or a transition metal oxide, or a combination of at least two of the following, typical but non-limiting examples being: al (Al)2O3And a transition metal oxide, MgO and a transition metal oxide, a transition metal oxide and a transition metal oxide or Al2O3And combinations of MgO and the like.
According to the invention, the positive pole piece comprises a lithium supplement material, and is co-sintered or doped with a metal oxide in the lithium supplement material, so that the oxygen element is inhibited from being removed, the oxygen release is reduced, the stability of the battery is improved, the high-coulombic-efficiency positive pole material is compounded with the lithium supplement material to prepare the high-energy-density positive pole material, and the energy density can reach 250-290 Wh/kg.
As a preferred technical scheme of the invention, MO in the positive pole piecez：Li5FeO4The mass ratio of (0.01-0.05): (0.1 to 15), wherein the mass ratio may be 0.01:0.1, 0.02:0.5, 002:2, 002:5, 0.03:8, 0.04:10, 0.04:12, or 0.05:15, but is not limited to the enumerated values, and other non-enumerated values within the numerical range are also applicable, and preferably (0.03 to 0.05): (2-5).
Preferably, the transition metal oxide comprises TiO2、SrO、ZrO2BaO or Y2O3Any one or a combination of at least two of the following, typical but non-limiting examples being: TiO 22And SrO, SrO and ZrO2Combination of (A) and (B), ZrO2And BaO or BaO and Y2O3Combinations of (a), (b), and the like.
Preferably, the positive electrode material is LiNixCoyMn1-x-yO2Or LiFePO40.5. ltoreq. x.ltoreq.0.9, 0. ltoreq. y.ltoreq.0.20, where the value of x can be 0.5, 0.6, 0.7, 0.8 or 0.9 etc., but is not limited to the values listed, and other values not listed in the numerical range are equally applicable, where the value of y can be 0.01, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18 or 0.20 etc., but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the mass ratio of the lithium supplement material to the positive electrode material is (0.1-10): (90-99), wherein the mass ratio may be 0.1: 90. 2: 92. 4: 94. 6: 96. 8: 98 or 10: 99, etc., but not limited to the recited values, and other values not recited within the numerical range are also applicable, and (1 to 2): (95-99).
As a preferred embodiment of the present invention, the LiNi isxCoyMn1-x-yO2Is in a secondary spherical form or a single crystal form.
Preferably, the LiNixCoyMn1-x-yO2The D50 particle size of the secondary sphere form is 9-25 μm, and the D50 particle size may be 9 μm, 11 μm, 13 μm, 15 μm, 17 μm, 19 μm, 21 μm, 23 μm or 25 μm, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the LiNixCoyMn1-x-yO2The grain diameter of the D50 in the single crystal form is 1.5-6 mu m, and preferably, the LiNixCoyMn1-x-yO2The grain size of the single crystal form of D50 may be 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm or 6 μmAnd the like, but not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferable technical scheme of the invention, the LiFePO is prepared by4The material of (2) is spherical lithium iron phosphate or nano lithium iron phosphate.
Preferably, the spherical lithium iron phosphate has a D50 particle size of 5 to 15 μm, and the D50 particle size may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Preferably, the nano lithium iron phosphate has a D50 particle size of 0.3 to 2.4 μm, and the D50 particle size may be 0.3 μm, 0.5 μm, 0.7 μm, 0.9 μm, 1.1 μm, 1.3 μm, 1.5 μm, 1.7 μm, 1.9 μm, 2.1 μm, 2.3 μm, or 2.4 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
As a preferred technical solution of the present invention, the positive electrode sheet further includes a positive electrode material, a conductive agent, a solvent, and an adhesive, preferably, the conductive agent is conductive carbon black and/or conductive carbon tubes, and preferably, a combination of the conductive carbon black and the conductive carbon tubes.
Preferably, the solvent is nitrogen methyl pyrrolidone.
Preferably, the binder is polyvinylidene fluoride.
As a preferred technical scheme of the invention, the mass ratio of the raw materials of the positive pole piece is as follows: lithium supplement materials: a positive electrode material: conductive agent: solvent: the binder is (0.1-10): (90-99): (1.4-1.6): (38-42): (0.8-1.2), wherein the mass ratio may be 0.1: 90: 1.4: 38: 0.8, 2: 92: 1.5: 39: 0.9, 4: 94: 1.6: 40: 1. 6: 96: 1.5: 41: 1.2, 8: 98: 1.5: 42: 1.2 or 10: 99: 1.6: 42: 1.2, etc., but not limited to the recited values, and other values not recited within the numerical range are also applicable, and (1 to 2): (95-99): (1.45-1.55): (39-41): (0.9 to 1.1), more preferably 2: 99: 1.5: 40: 1.
preferably, the mass ratio of the conductive carbon black to the conductive carbon tubes in the conductive agent is (1-3): 1, wherein the mass ratio can be 1: 1. 2: 1 or 3: 1, etc., but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
The second objective of the present invention is to provide a method for preparing the positive electrode plate according to the first aspect, wherein the method comprises the following steps:
(1) mixing the lithium supplement material and the anode material to prepare mixed active substance powder;
(2) mixing other raw materials of the positive pole piece to prepare conductive slurry;
(3) mixing the active material powder and the conductive slurry to prepare positive electrode slurry;
(4) and uniformly coating the positive electrode slurry to prepare the positive electrode plate.
According to the invention, the lithium supplement material and the anode material are mixed to prepare the composite electrode plate, and the prepared electrode plate has high energy density.
As a preferable technical scheme of the invention, other raw materials of the positive pole piece in the step (2) comprise a conductive agent, a solvent and an adhesive.
Preferably, the mixing speed in steps (1) - (3) is 800-2000 rpm, which can be 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm, 1900rpm, 2000rpm, etc., but is not limited to the recited values, and other non-recited values in the range are also applicable.
Preferably, the mixing in steps (1) - (3) is independently performed for 1.5-2.5 h, and the mixing time can be 1.5h, 1,6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h or 2.5h, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the coating in the step (4) is followed by standing for drying.
Preferably, the temperature of the standing and drying in the step (4) is 100 to 150 ℃, and the temperature may be 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the standing and drying time in step (4) is 15-25 min, and the time may be 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min or 25min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the standing and drying are followed by rolling and cutting.
Preferably, the rolling pressure in step (4) is 15 to 25MPa, and the pressure may be 15MPa, 16MPa, 17MPa, 18MPa, 19MPa, 20MPa, 21MPa, 22MPa, 23MPa, 24MPa or 25MPa, but is not limited to the recited values, and other values not recited in the above range are also applicable.
As a preferable technical scheme of the invention, the preparation method of the lithium supplement material comprises the step of mixing MOzOr MOzBy blending or co-sintering the precursors of (A) to (B) to introduce Li5FeO4。
Preferably, the MOzThe precursor of (A) is hydroxide or acetate of corresponding metal.
Preferably, the blending means includes dry mixing and wet mixing,
preferably, the mixing is carried out at a stirring rate of 800 to 2200r/min, wherein the stirring rate may be 800r/min, 1000r/min, 1200r/min, 1400r/min, 1600r/min, 1800r/min, 2000r/min, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mixing is performed for 30-240 min, wherein the time can be 30min, 60min, 90min, 120min, 150min, 180min, 210min or 240min, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the co-sintering temperature is 650 to 800 ℃, and the temperature may be 650 ℃, 670 ℃, 690 ℃, 710 ℃, 730 ℃, 750 ℃, 770 ℃, 790 ℃ or 800 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable, and more preferably 700 to 750 ℃.
Preferably, the co-sintering time is 16-40h, and the co-sintering time can be 16h, 20h, 25h, 30h, 35h or 40h, but is not limited to the recited values, and other values not recited in the numerical range are also applicable, and more preferably 25-32 h.
The third objective of the present invention is to provide an application of the positive electrode plate according to the first aspect, wherein the positive electrode plate is applied to the field of lithium ion batteries.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention adopts the positive electrode material with high coulombic efficiency and the lithium supplement material to compound, and prepares the positive electrode material with high energy density, and the energy density can reach more than 250 Wh/kg. The lithium supplement material is co-sintered or doped with metal oxide, so that the removal of oxygen is inhibited, the release of oxygen is reduced, and the gas production in the storage process of the battery is reduced to be less than 5% in 56 days. The stability of the battery is improved.
Drawings
FIG. 1 is a graph of gas production as a function of days on storage for example 1 and comparative example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
In the prior art, one technical solution provides a lithium ion battery, and the positive electrode material of the lithium ion battery is selected from LiNixM1-xO2Wherein M is selected from any one or the combination of at least two of Co, Mn, Al, Mg, Ti, Zr or B, the additive of the electrolyte comprises a sulfone compound, and the sulfone compound in the electrolyte and the high-nickel positive electrodeThe surface of the material reacts to finally form a protective layer, and the formed protective layer can reduce the catalytic decomposition of transition metal ions on the surface of the anode material on the electrolyte, so that the gas production of the lithium ion battery in high-temperature storage is reduced, and the lithium ion battery has good cycle performance and high-temperature storage performance. Although the lithium ion battery has good cycle performance and high-temperature storage performance under the method, the LFO material and the solution of the LFO material for inhibiting the oxygen release are not mentioned.
The other technical scheme provides a lithium supplement additive for a lithium ion anode material and a preparation method thereof, and the lithium supplement additive comprises two coating layers, wherein the first coating layer is a carbon coating layer, the second coating layer is a transition metal oxide coating layer, and the double coating layers can realize the exertion of lithium supplement performance of an LFO material and prolong the service life of a lithium ion battery. This is because Li5FeO4Active O on the surface of the particles2-Is easy to react with CO in the air2And H2Reaction of O to form CO3 2-And OH-And forming Li on the surface of the material2CO3And LiOH, so that a layer of transition metal oxide is coated on the surface of LFO, and stable Li can be formed on the surface of the LFO5Fe1-xMxO4The solid-solution interface reduces the direct contact between the material and the outside air, and effectively isolates moisture and carbon dioxide. Although the technical scheme isolates the problem of contact between the LFO and air, the problem of inhibiting the release of oxygen in the LFO is not solved.
The other technical scheme provides a high residual alkali lithium ion multi-element anode material and a preparation method thereof. The raw material comprises LiaNixCoyMn1-x-yAzO2A is any one or combination of at least two of Cr, La, Ce, Zr, Mg, Al, W, V, Be, Y, Mo, Tb, Ho or Tm oxides, the high-residual-alkali positive electrode material is obtained in a sintering mode, the cation mixed-discharge phenomenon is reduced, the structure is stabilized, the overcharge safety performance of the steel shell battery can Be improved, and the electrochemical performance of the steel shell battery is improved. The technical scheme provides a sintering mode, and the phenomenon of cation mixed discharge is reduced through sintering, so thatThe structure of the meta-anode material is more stable.
However, there is no mention in the prior art of how to effectively increase the energy density of a lithium ion battery and to improve the stability of the battery in storage cycles. The technical problem is an important research direction in the field of lithium ion battery anode materials.
In order to solve at least the technical problems, the invention provides a technical scheme of a positive pole piece of a high-energy-density lithium ion battery. The positive pole piece comprises a lithium supplement material and a positive pole material. By co-sintering or doping metal oxide in the lithium supplement material, the removal of oxygen element can be inhibited, thereby reducing the release of oxygen and improving the stability of the battery.
Example 1
The positive pole piece is prepared by the following steps:
(1) according to Al2O3-Li5FeO4And LiNi in the form of secondary spheres0.8Co0.1Mn0.1O2The mass ratio is 2: 99 preparing raw materials, and then stirring the mixture for 2 hours at a stirring speed of 1400rmp to prepare the active substance blended powder, wherein the Al is2O3With Li5FeO4Is 0.05: 2;
(2) mixing the components in a mass ratio of 1: 0.5: 40: 1 Super P, CNT, NMP, PVDF were stirred for 2 hours at a stirring rate of 1400rmp to prepare a conductive slurry;
(3) mixing the active substance powder and the conductive slurry, and stirring at a stirring speed of 1400rmp for 2 hours to prepare anode slurry;
(4) and uniformly coating the anode slurry on an aluminum foil, standing and drying at 120 ℃ for 20 minutes, and rolling and cutting under 15MPa to prepare the anode electrode plate.
The preparation method of the lithium supplement material in the step (1) comprises the following steps:
mixing Al2O3Stirring at a stirring speed of 800r/min for 240min, and introducing Li by dry mixing and stirring5FeO4。
Example 2
The positive pole piece is prepared by the following steps:
(1) according to MgO-Li5FeO4And LiNi in the form of a single crystal0.8Co0.1Mn0.1O2The mass ratio is 0.1: 90 preparing raw materials, and then stirring for 2.5 hours at a stirring speed of 800rmp to prepare active substance blending powder; the MgO and Li5FeO4Is 0.01: 0.1;
(2) mixing the components in a mass ratio of 1: 0.5: 38: 0.8 of Super P, CNT, NMP, PVDF was stirred for 2.5 hours at a stirring rate of 800rmp to prepare a conductive slurry;
(3) mixing the active substance powder and the conductive slurry, and stirring at a stirring speed of 800rmp for 2.5 hours to prepare anode slurry;
(4) and uniformly coating the anode slurry on an aluminum foil, standing and drying at 100 ℃ for 25 minutes, and rolling and cutting under 25MPa to prepare the anode electrode plate.
The preparation method of the lithium supplement material in the step (1) comprises the following steps:
stirring MgO at the stirring speed of 2200r/min for 30min, and introducing Li by wet mixing stirring and blending5FeO4。
Example 3
The positive pole piece is prepared by the following steps:
(1) according to SrO-Li5FeO4And LiNi in the form of secondary spheres0.8Co0.1Mn0.1O2The mass ratio is 10: 99 and then stirring the mixture for 2.3h at a stirring speed of 1100rmp to prepare the active material powder, wherein the SrO and the Li are mixed5FeO4The mass ratio of (A) to (B) is 0.05: 15;
(2) mixing the components in a mass ratio of 1: 05: 42: 1.2 Super P, CNT, NMP and PVDF are stirred for 2.3h at the stirring speed of 1100rmp to prepare conductive slurry;
(3) mixing the active substance powder and the conductive slurry, and stirring at a stirring speed of 1100rmp for 2.3h to prepare anode slurry;
(4) and uniformly coating the anode slurry on an aluminum foil, standing and drying at 110 ℃ for 23 minutes, and rolling and cutting under 20MPa to prepare the anode electrode plate.
The preparation method of the lithium supplement material in the step (1) comprises the following steps:
sintering SrO at the co-sintering temperature of 650 ℃ for 40h, and introducing Li5FeO4。
Example 4
The positive pole piece is prepared by the following steps:
(1) according to ZrO2-Li5FeO4With spherical LiFePO4The mass ratio is 1: 95 preparing raw materials, and then stirring for 1.5 hours at a stirring speed of 2000rmp to prepare active substance blending powder; the SrO is in contact with Li5FeO4In a mass ratio of 0.03:2
(2) Mixing the components in a mass ratio of 1: 0.5: 39: 0.9 of Super P, CNT, NMP and PVDF are stirred for 1.5h at the stirring speed of 2000rmp to prepare conductive slurry;
(3) mixing the active substance powder and the conductive slurry, and stirring at a stirring speed of 2000rmp for 1.5h to prepare anode slurry;
(4) and uniformly coating the positive electrode slurry on an aluminum foil, standing and drying at 130 ℃ for 17 minutes, rolling under 17MPa, and cutting to prepare the positive electrode slice.
The preparation method of the lithium supplement material in the step (1) comprises the following steps:
sintering SrO at 800 ℃ of co-sintering temperature for 16h, and introducing Li5FeO4。
Example 5
The positive pole piece is prepared by the following steps:
(1) according to Y2O3-Li5FeO4With nano-LiFePO4The mass ratio is 2: 97 and then stirred for 1.7h at a stirring speed of 1700rmp to prepare the blended active material powder, Y2O3With Li5FeO4Is 0.05: 5.
(2) mixing the components in a mass ratio of 1: 0.5: 41: 1.1 stirring Super P, CNT, NMP and PVDF for 1.7h at a stirring speed of 1700rmp to prepare conductive slurry;
(3) mixing the active substance powder and the conductive slurry, and stirring at a stirring speed of 1700rmp for 1.7h to prepare anode slurry;
(4) and uniformly coating the anode slurry on an aluminum foil, standing and drying at 150 ℃ for 15 minutes, and rolling and cutting under 22MPa to prepare the anode electrode plate.
The preparation method of the lithium supplement material in the step (1) comprises the following steps:
sintering SrO at the co-sintering temperature of 700 ℃ for 32h, and introducing Li5FeO4。
Example 6
Mixing Al2O3With LiNi in the form of secondary spheres0.8Co0.1Mn0.1O2The mass ratio of (2) was changed to 0.01:16, and the rest was the same as in example 1.
Example 7
Mixing Al2O3With LiNi in the form of secondary spheres0.8Co0.1Mn0.1O2The mass ratio of (2) was changed to 0.06:0.09, and the rest was the same as in example 1.
Example 8
Mixing Al2O3-Li5FeO4And LiNi in the form of secondary spheres0.8Co0.1Mn0.1O2The mass ratio of (2) was changed to 11:80, and the rest was the same as in example 1.
Example 9
Mixing Al2O3-Li5FeO4And LiNi in the form of secondary spheres0.8Co0.1Mn0.1O2The mass ratio of (a) to (b) is changed to 0.09: 110, the rest is the same as in example 1.
Example 10
The mass ratio of Super P, CNT, NMP and PVDF is changed to 1: 0.5: 37: 1.3, the rest are the same as in example 1.
Example 11
The mass ratio of Super P, CNT, NMP and PVDF is changed to 1: 0.5: 43: 0.7, and the rest are the same as in example 1.
Example 12
Will supplement Al in the lithium material2O3Substituted by TiO2After that, itHe is the same as in example 1.
Example 13
Will supplement Al in the lithium material2O3Replacement by SiO2Thereafter, the rest was the same as in example 1.
Example 14
Will supplement Al in the lithium material2O3The procedure was repeated except for replacing BaO with BaO in the same manner as in example 1.
Comparative example 1
This comparative example did not contain Al except for the lithium supplement material2O3Otherwise, the other conditions were the same as in example 1.
It can be seen from fig. 1 that the gas production of example 1 is significantly reduced compared to that of comparative example 1.
Comparative example 2
This comparative example was conducted except that Al in the lithium-doped material was replaced2O3The procedure of example 1 was repeated except that CaO was used instead of CaO.
Comparative example 3
This comparative example was the same as example 1 except that no lithium supplement material was added.
The gas production rates of the positive electrode sheets provided in examples 1 to 14 and comparative examples 1 to 3 were measured, and the results are shown in table 1.
The method for testing the gas production rate of the positive pole piece comprises the following steps:
the positive electrode sheets prepared in examples 1 to 14 and comparative examples 1 to 3 were assembled into a 1Ah pouch battery, which was charged to a voltage of 4.3V at a rate of 3.3C at room temperature after formation and aging processes, and the initial volume V of the battery was recorded by a drainage method0Then the cells were stored in a constant temperature oven at 60 ℃, removed from the oven every 7 days, allowed to stand to room temperature, the volume of the cells tested, and the cells were recharged to 4.25V at 0.33C rate. The volume of the battery changes according to the gas production rate of the battery core.
The energy density is calculated as the gram capacity multiplied by the median voltage of discharge of the cell.
TABLE 1
Figure BDA0003240044080000131
Figure BDA0003240044080000141
From the above results, it can be seen that examples 1, 2, 4, 5, 12, 13 and 14 changed the mixed oxides, had significantly reduced gas production storage amounts as compared with comparative examples 1 and 2, and had improved energy density as compared with comparative example 3. Examples 3, 6 and 8 increase the proportion of lithium supplement additive, which significantly increases the energy density and reduces the gas production compared to comparative example 1. Examples 7 and 9 have improved energy density and reduced gas production stored compared to comparative example 3. The examples 10 and 11 adjust the amount of PVDF, and the energy density and the storage gas generation are better than those of the comparative example 1, so that the improvement scheme can adapt to various PVDF formula proportions.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The positive pole piece of the high-energy-density lithium ion battery is characterized by comprising a lithium supplement material and a positive pole material, wherein the lithium supplement material is MOzWith Li5FeO4Mixture of (A), the MOzIncluding Al2O3、MgO、SiO2Or a combination of at least two of the transition metal oxides.
2. The positive electrode sheet according to claim 1, wherein the MO is disposed in the negative electrode layerzWith said Li5FeO4The mass ratio of (1) to (0.01-0).05): (0.1-15), preferably (0.03-0.05): (2-5);
preferably, the transition metal oxide comprises TiO2、SrO、ZrO2BaO or Y2O3Any one or a combination of at least two of;
preferably, the cathode material has a general formula of LiNixCoyMn1-x-yO2Or LiFePO4Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.20;
preferably, the mass ratio of the lithium supplement material to the cathode material is (0.1-10): (90-99), preferably (1-2): (95-99).
3. The positive electrode sheet according to claim 1 or 2, wherein the LiNi isxCoyMn1-x-yO2Is in a secondary spherical form or a single crystal form;
preferably, the LiNixCoyMn1-x-yO2The grain diameter of the secondary ball D50 is 9-25 μm;
preferably, the LiNixCoyMn1-x-yO2The grain size of the single crystal form D50 is 1.5 to 6 μm.
4. The positive electrode sheet according to any one of claims 1 to 3, wherein the LiFePO is4The material of (a) is spherical lithium iron phosphate or nano lithium iron phosphate;
preferably, the D50 particle size of the spherical lithium iron phosphate is 5-15 μm;
preferably, the D50 particle size of the nano lithium iron phosphate is 0.3-2.4 μm.
5. The positive electrode plate according to any one of claims 1 to 4, wherein the raw materials of the positive electrode plate further comprise a conductive agent, a solvent and a binder;
preferably, the conductive agent is conductive carbon black and/or conductive carbon tubes, preferably a combination of conductive carbon black and conductive carbon tubes;
preferably, the solvent is nitrogen methyl pyrrolidone;
preferably, the binder is polyvinylidene fluoride.
6. The positive pole piece according to claim 5, wherein the mass ratio of the raw materials of the positive pole piece is as follows: lithium supplement materials: a positive electrode material: conductive agent: solvent: the binder is (0.1-10): (90-99): (1.4-1.6): (38-42): (0.8-1.2), preferably (1-2): (95-99): (1.45-1.55): (39-41): (0.9 to 1.1);
preferably, the mass ratio of the conductive carbon black to the conductive carbon tubes in the conductive agent is (1-3): 1.
7. The preparation method of the positive pole piece according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) mixing the lithium supplement material and the anode material to prepare mixed active substance powder;
(2) mixing other raw materials of the positive pole piece to prepare conductive slurry;
(3) mixing the active material powder and the conductive slurry to prepare positive electrode slurry;
(4) and uniformly coating the positive electrode slurry to prepare the positive electrode plate.
8. The preparation method according to claim 7, wherein other raw materials of the positive electrode sheet in the step (2) comprise a conductive agent, a solvent and a binder;
preferably, the mixing stirring rates in the steps (1) to (3) are respectively and independently 800-2000 rpm;
preferably, the mixing in the steps (1) to (3) is independently performed for 1.5 to 2.5 hours;
preferably, standing and drying are carried out after the coating in the step (4);
preferably, the temperature of the standing drying is 100-150 ℃;
preferably, the standing and drying time is 15-25 min;
preferably, rolling and cutting treatment are carried out after the standing and drying;
preferably, the rolling pressure is 15-25 MPa.
9. The method according to claim 7 or 8, wherein the lithium-supplementing material is prepared by mixing MOzOr MOzBy blending or co-sintering the precursors of (A) to (B) to introduce Li5FeO4；
Preferably, the MOzThe precursor of (A) is hydroxide or acetate of corresponding metal;
preferably, the blending manner includes dry mixing and wet mixing;
preferably, the stirring speed of the mixing is 800-2200 r/min;
preferably, the mixing time is 30-240 min;
preferably, the co-sintering temperature is 650-800 ℃, and further preferably 700-750 ℃;
preferably, the co-sintering time is 16-40h, and further preferably 25-32 h.
10. The application of the positive pole piece according to any one of claims 1 to 6, wherein the positive pole piece is applied to the field of lithium ion batteries.
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