CN113097453A - Lithium pre-embedding method for positive electrode of lithium ion battery - Google Patents

Lithium pre-embedding method for positive electrode of lithium ion battery Download PDF

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CN113097453A
CN113097453A CN202010021971.XA CN202010021971A CN113097453A CN 113097453 A CN113097453 A CN 113097453A CN 202010021971 A CN202010021971 A CN 202010021971A CN 113097453 A CN113097453 A CN 113097453A
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lithium
ion battery
positive electrode
lithium ion
electrode
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孟焕菊
王振
路艳
张阳
屈国莹
杨道均
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RiseSun MGL New Energy Technology Co Ltd
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RiseSun MGL New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1397Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01M4/00Electrodes
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    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
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    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5805Phosphides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a lithium pre-embedding method for a lithium ion battery anode electrode, which comprises the following steps: manufacturing a conductive liquid; mixing the following components in percentage by mass (0.99-0.85): (0.01-0.15) Positive electrode active Material and Li3Adding the P powder into the conductive liquid and stirring to obtain electrode liquid; and coating the electrode solution on an aluminum foil to obtain the pre-lithium-embedded positive pole piece. The method for pre-embedding lithium provided by the invention is simpleThe lithium ion battery anode material is simple and easy to implement, can be directly applied to the existing lithium ion battery mixing and pulping process, is low in manufacturing cost without adding extra production equipment, can effectively provide an extra lithium source at the anode to supplement lithium lost due to SEI film formation in the first charging and discharging process, reduces irreversible capacity and improves energy density.

Description

Lithium pre-embedding method for positive electrode of lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium pre-embedding method for a positive electrode of a lithium ion battery.
Background
In recent years, with national support and vigorous popularization of new energy industries, market share of new energy automobiles is gradually increased, and national subsidy policies are more and more inclined to high-energy-density batteries in order to eliminate anxiety of people on the endurance mileage of electric automobiles, so that the high-energy-density batteries are produced at the same time.
The conventional negative electrode material for the lithium ion battery is graphite, the graphite material has good cycling stability but low theoretical specific capacity, and the requirement of the high-energy density battery is difficult to meet, so that the silicon-based negative electrode material with higher theoretical specific capacity is widely concerned by researchers. Pure silicon materials undergo a volume expansion of 300-400% during the lithium ion deintercalation process, which leads to rapid pulverization of active materials, failure of contact in electrodes, and repeated generation of new solid electrolyte layer SEI films, ultimately resulting in a reduction in cycle life. In order to improve the cycle stability of the silicon negative electrode, various modifications have been made by researchers. Wherein, silicon oxide (SiO)x,0<x<2) The high specific capacity and the good cycling stability attract special attention of people. However, the material can consume a large amount of electrolyte and lithium ions in the positive active material in the first charge-discharge process, so that the first coulombic efficiency is low, the irreversible capacity is large, the energy density of the battery is greatly reduced, and the SiO is also severely restrictedxThe negative electrode material is applied to the high specific energy lithium ion battery. The lithium pre-intercalation technology is considered as an effective means for reducing irreversible capacity and increasing energy density at present.
In view of the above, it is desirable to provide a method for pre-embedding lithium, which is simple in operation and low in manufacturing cost, and can effectively supplement lithium consumed by the SEI film formation in the first charging and discharging process, reduce the irreversible capacity, and increase the energy density.
Disclosure of Invention
In order to solve the technical problems, the technical scheme adopted by the invention is to provide a lithium pre-embedding method for a positive electrode of a lithium ion battery, which comprises the following steps:
s1, preparing a conductive liquid;
s2, mixing the components in a mass ratio of (0.99-0.85): (0.01-0.15) Positive electrode active Material and Li3Adding the P powder into the conductive liquid and stirring to obtain electrode liquid;
and S3, coating the electrode solution on an aluminum foil to obtain the lithium pre-embedded positive pole piece.
In the above method, the step S3 includes the steps of:
s31, removing bubbles from the electrode solution;
and S32, coating the electrode solution obtained in the step S31 on an aluminum foil, and drying to obtain the lithium pre-embedded positive electrode piece.
In the above method, in the step S2, the stirring time is 2-5 h.
In the method, the binder is one or a mixture of PVDF powder and PTFE powder.
In the method, the positive active material is one or a mixture of more of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide and lithium iron phosphate.
In the above method, the step S1 specifically includes the following steps:
s11, adding the binder into NMP to prepare a binder solution;
and S12, adding the conductive agent into the binder solution and mixing to obtain the conductive liquid.
In the method, the mass concentration of the binder solution is 4-10%.
In the above method, the conductive agent accounts for the binder, the conductive agent, the positive electrode active material and Li by mass31-5% of the total mass of the P powder.
In the method, the mixing time in the step S12 is 1-4 h.
In the above method, the conductive agent in step S12 is one or more of acetylene black, Super P, VGCF, carbon nanotube, carbon nanofiber, and graphene.
The pre-lithium embedding method provided by the invention is simple and feasible, can be directly applied to the existing lithium ion battery mixing and pulping process, is low in manufacturing cost without adding extra production equipment, and can effectively provide an extra lithium source at the positive electrode so as to supplement lithium lost due to SEI film formation in the first charging and discharging process, reduce irreversible capacity and improve energy density.
Drawings
FIG. 1 is a flow chart provided by the present invention.
Detailed Description
The invention is described in detail below with reference to specific embodiments and the accompanying drawings.
As shown in fig. 1, the invention provides a lithium pre-embedding method for a positive electrode plate of a lithium ion battery, which comprises the following steps:
s1, preparing a conductive liquid;
s2, mixing the components in a mass ratio of (0.99-0.85): (0.01-0.15) Positive electrode active Material and Li3Adding the P powder into the conductive liquid and stirring to obtain electrode liquid;
and S3, coating the electrode solution on an aluminum foil to obtain the lithium pre-embedded positive pole piece.
In the embodiment, the pre-lithium-embedded positive pole piece prepared by the method is simple in preparation method, can be directly applied to the existing lithium ion battery mixing and pulping process, is low in preparation cost without adding extra production equipment, and can effectively provide an extra lithium source on the positive pole so as to supplement lithium lost due to SEI film formation in the first charging and discharging process, reduce irreversible capacity and improve energy density.
In this embodiment, step S1 specifically includes the following steps:
s11, adding the binder into NMP to prepare a binder solution; the mass concentration of the binder solution is 4-10%.
And S12, adding the conductive agent into the binder solution and mixing to obtain the conductive liquid.
Wherein (cathode active material + Li)3P): conductive agent: the mass ratio of the binder to the binder is (0.92-0.98): (0.01-0.05): (0.01-0.03).
In this embodiment, step S3 specifically includes the following steps:
s31, removing bubbles from the electrode solution; in this embodiment, the bubbles in the electrode liquid can be removed by a slow stirring method in a vacuum environment.
And S32, coating the electrode solution obtained in the step S31 on an aluminum foil, and drying to obtain the lithium pre-embedded positive electrode piece. Wherein the drying condition is that the baking can be carried out for 4-10h at 90-120 ℃ by a drying oven.
In this embodiment, in step S2, the stirring time is preferably 2-5 h.
In this embodiment, the binder is preferably one or a mixture of PVDF powder and PTFE powder.
In this embodiment, the conductive agent is preferably one or a mixture of acetylene black, Super P, VGCF, carbon nanotube, carbon nanofiber, and graphene.
In this embodiment, the mixing time after the addition is preferably 1 to 4 hours in order to sufficiently mix the conductive agent into the binder solution.
In the preferred embodiment, the conductive agent comprises the binder, the conductive agent, the positive electrode active material and Li31-5% of the total mass of the P powder. In the embodiment, the influence of the proportion of the conductive agent is the conductivity of the pole piece, and different types of batteries have different requirements on the content of the conductive agent in the pole piece, so that the proportion of the conductive agent is required. In addition, because NMP can be evaporated in the drying process, the finally obtained pre-embedded lithium pole piece does not contain NMP and only contains the binder, the conductive agent, the positive active material and Li3The mass of the P powder can be ignored, and only the initial adding amount of the four substances is needed to be determined in the whole process of manufacturing the electrode liquid.
In this embodiment, the positive electrode active material is preferably one or a mixture of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, and lithium iron phosphate.
In the preferred embodiment, the surface density of the electrode solution is 100-600g/m2Coating on aluminum foil.
The preparation process of the present invention is described below by way of specific examples.
Example 1.
Adding NMP into PVDF powder to prepare a binder solution with the mass concentration of 7%, wherein the PVDF powder accounts for 1.5% of the total mass of the powder, adding Super P accounting for 2% of the total mass of the powder into the binder solution, mixing for 1h to prepare a conductive solution, and adding LiNi with the mass ratio of 94:6 into the conductive solution1/3Co1/3Mn1/3O2(NCM333) and Li3Adding P powder into the conductive liquid, and continuously stirring for 2h, wherein LiNi1/ 3Co1/3Mn1/3O2And Li3The P powder accounts for 96.5 percent of the total mass of the powder. After stirring to remove bubbles, the density of the mixture is 300g/m2Coating the lithium-containing anode plate on an aluminum foil, and drying to obtain the lithium-embedded anode plate. Wherein the total mass of the powder refers to binder, conductive agent, positive electrode active material and Li3The total mass of P powder;
and rolling and cutting the obtained positive pole piece into a 14mm wafer. Assembling into button type half cell in argon glove box, wherein the counter electrode is Li piece, and the electrolyte is 1.0mol/LLIPF6(EC + DEC + DMC (volume ratio of 2:2:1)), wherein the electrolyte comprises a solvent and a solute, the solvent is EC + DEC + DMC, the volume ratio of the solvent to DEC + DMC is 2:2:1, and the solute is LiPF61mol of LiPF is dissolved in 1L of solvent6And the diaphragm is Cellgard-2340.
Example 2.
Adding NMP into PVDF powder to prepare a binder solution with the mass concentration of 4%, wherein the PVDF powder accounts for 3% of the total mass of the powder, and adding 5% of acetylene black into the binder solution to mix for 4 hours to prepare the conductive liquid. LiCoO with the mass ratio of 85:152And Li3Adding the P powder into the conductive liquid, and continuously stirring for 4 hours, wherein LiCoO2And Li3The P powder accounts for 92 percent of the total mass of the powder. After stirring to remove bubbles, the density of the mixture is 600g/m2Coating the lithium-containing anode plate on an aluminum foil, and drying to obtain the lithium-embedded anode plate.
And rolling and cutting the obtained positive pole piece into a 14mm wafer. Assembling into button type half cell in argon glove box, wherein the counter electrode is Li piece, and the electrolyte is 1.0mol/LLIPF6/(EC + DEC + DMC (2: 2:1 by volume)), and the separator is Cellgard-2340.
Example 3.
Adding NMP into PTFE powder to prepare a binder solution with the mass concentration of 10%, wherein the PTFE powder accounts for 1% of the total mass of the powder, adding VGCF accounting for 1% of the total mass of the powder into the binder solution, and mixing for 2 hours to obtain the conductive liquid. LiFePO with the mass ratio of 99:14And Li3Adding the P powder into the conductive liquid, and continuously stirring for 5 hours, wherein the LiFePO is formed4And Li3The P powder accounts for 98 percent of the total mass of the powder. After stirring to remove bubbles, the density of the mixture is 100g/m2Coating the lithium-containing anode plate on an aluminum foil, and drying to obtain the lithium-embedded anode plate.
And rolling and cutting the obtained positive pole piece into a 14mm wafer. Assembling into button type half cell in argon glove box, wherein the counter electrode is Li piece, and the electrolyte is 1.0mol/LLIPF6/(EC + DEC + DMC (2: 2:1 by volume)), and the separator is Cellgard-2340.
The following table shows the comparison between the positive electrode sheet manufactured by the above 3 examples and the positive electrode sheet manufactured by using the positive active material alone, the first charge capacity, the first discharge capacity, the first effect (first discharge capacity/first charge capacity), and the specific charge capacity increase per unit mass (the capacity increase means a specific capacity higher than the first charge without lithium supplement after lithium supplement).
TABLE 1 data results in different examples
Figure BDA0002361131130000061
The above-described embodiments are merely preferred embodiments of the present invention, and are not intended to limit the present invention in any way.
The present invention is not limited to the above-mentioned preferred embodiments, and any structural changes made under the teaching of the present invention shall fall within the protection scope of the present invention, which has the same or similar technical solutions as the present invention.

Claims (10)

1. A lithium pre-embedding method for a positive electrode of a lithium ion battery is characterized by comprising the following steps:
s1, preparing a conductive liquid;
s2, mixing the components in a mass ratio of (0.99-0.85): (0.01-0.15) Positive electrode active Material and Li3Adding the P powder into the conductive liquid and stirring to obtain electrode liquid;
and S3, coating the electrode solution on an aluminum foil to obtain the lithium pre-embedded positive pole piece.
2. The method for pre-inserting lithium into the positive electrode of the lithium ion battery according to claim 1, wherein the step S3 comprises the following steps:
s31, removing bubbles from the electrode solution;
and S32, coating the electrode solution obtained in the step S31 on an aluminum foil, and drying to obtain the lithium pre-embedded positive electrode piece.
3. The method for pre-intercalating lithium into the positive electrode of the lithium ion battery according to claim 1 or 2, wherein the stirring time in step S2 is 2-5 h.
4. The method for pre-embedding lithium into the positive electrode of the lithium ion battery as claimed in claim 1 or 2, wherein the binder is one or a mixture of PVDF powder and PTFE powder.
5. The method for pre-embedding lithium into the positive electrode of the lithium ion battery according to claim 1 or 2, wherein the positive active material is one or more of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide and lithium iron phosphate.
6. The method for pre-embedding lithium into the positive electrode of the lithium ion battery according to claim 1, wherein the step S1 specifically comprises the following steps:
s11, adding the binder into NMP to prepare a binder solution;
and S12, adding the conductive agent into the binder solution and mixing to obtain the conductive liquid.
7. The method for pre-intercalating lithium into the positive electrode of the lithium ion battery according to claim 6, wherein the mass concentration of the binder solution is 4% to 10%.
8. The method for pre-intercalating lithium in the positive electrode of lithium ion battery according to claim 6 or 7, wherein the conductive agent comprises a binder, a conductive agent, a positive active material and Li31-5% of the total mass of the P powder.
9. The method for pre-inserting lithium into the positive electrode of the lithium ion battery according to claim 6, wherein the mixing time in the step S12 is 1-4 h.
10. The method for pre-embedding lithium into the positive electrode of the lithium ion battery according to claim 6, wherein the conductive agent in the step S12 is one or more of acetylene black, Super P, VGCF, carbon nanotubes, carbon nanofibers, and graphene.
CN202010021971.XA 2020-01-09 2020-01-09 Lithium pre-embedding method for positive electrode of lithium ion battery Pending CN113097453A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114944488A (en) * 2022-05-23 2022-08-26 浙江锂威能源科技有限公司 Preparation method of coated positive electrode material, product and application thereof

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CN110071265A (en) * 2019-04-02 2019-07-30 浙江工业大学 A kind of silicon-carbon cathode prelithiation method
CN110120493A (en) * 2018-02-07 2019-08-13 湖北猛狮新能源科技有限公司 A kind of lithium ion cell positive benefit lithium method

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WO2010072136A1 (en) * 2008-12-22 2010-07-01 深圳市比克电池有限公司 Positive material of lithium ion battery and method for preparing the same
CN105702913A (en) * 2014-11-27 2016-06-22 比亚迪股份有限公司 Positive electrode and preparation method therefor, and lithium secondary battery
DE202015104569U1 (en) * 2015-01-06 2015-09-17 Ningbo Csr New Energy Technology Co., Ltd. A New Anode and Cathode Composite Based Cell Capacitor
CN110120493A (en) * 2018-02-07 2019-08-13 湖北猛狮新能源科技有限公司 A kind of lithium ion cell positive benefit lithium method
CN108365174A (en) * 2018-03-23 2018-08-03 复旦大学 A kind of prelithiation method of anode material for lithium-ion batteries
CN110071265A (en) * 2019-04-02 2019-07-30 浙江工业大学 A kind of silicon-carbon cathode prelithiation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114944488A (en) * 2022-05-23 2022-08-26 浙江锂威能源科技有限公司 Preparation method of coated positive electrode material, product and application thereof
CN114944488B (en) * 2022-05-23 2024-02-09 浙江锂威能源科技有限公司 Preparation method of coated positive electrode material, product and application thereof

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Application publication date: 20210709