CN111063880A - Ternary high-rate polymer lithium ion battery and manufacturing method thereof - Google Patents

Ternary high-rate polymer lithium ion battery and manufacturing method thereof Download PDF

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Publication number
CN111063880A
CN111063880A CN201911059026.2A CN201911059026A CN111063880A CN 111063880 A CN111063880 A CN 111063880A CN 201911059026 A CN201911059026 A CN 201911059026A CN 111063880 A CN111063880 A CN 111063880A
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Prior art keywords
negative
positive
lithium ion
ion battery
ternary
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CN201911059026.2A
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Inventor
王大林
姜庆海
吴战宇
朱明海
施晓渝
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Huafu Jiangsu Lithium Electricity New Technology Co ltd
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Huafu Jiangsu Lithium Electricity New Technology Co ltd
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Publication of CN111063880A publication Critical patent/CN111063880A/en
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a ternary high-rate polymer lithium ion battery and a manufacturing method thereof, wherein the ternary high-rate polymer lithium ion battery comprises a positive plate, a negative plate and a shell, wherein the positive plate and the negative plate are laminated; the manufacturing method of the ternary high-rate polymer lithium ion battery comprises the following steps: 1. preparing a positive electrode, 2 preparing a negative electrode, 3 assembling a battery, and 4 forming and grading the battery. Compared with the traditional lithium cobalt oxide lithium ion battery, the lithium cobalt oxide lithium ion battery adopts the ternary material as the anode material, reduces the impedance value, improves the conductivity and the capacity, and has the advantages of good rate capability, good cycle performance and good safety while reducing the material cost.

Description

Ternary high-rate polymer lithium ion battery and manufacturing method thereof
Technical Field
The invention relates to a ternary high-rate polymer lithium ion battery and a manufacturing method thereof, belonging to the technical field of lithium ion batteries.
Background
The lithium ion battery has the advantages of high energy density, good rate performance and the like, and is widely applied to agricultural plant protection unmanned aerial vehicles, so that the spraying efficiency of pesticides is improved. As a pesticide spraying tool, the flight time and the service life of the plant protection unmanned aerial vehicle are important points, and the aspects mainly depend on the performance of a high-rate battery and are focused on the aspects of energy density, rate performance, cycle performance, safety performance and the like.
Lithium cobaltate is the lithium ion battery of cathode material for use on traditional plant protection unmanned aerial vehicle, and cathode material's price is with high costs, and this kind of lithium ion battery is at defects such as the in-process cycle life of using is short, the security performance is poor moreover, increases use cost, causes bodily injury easily even.
In view of this, it is necessary to develop a lithium ion battery with lower cost, better rate performance, longer cycle life and better safety to replace the application of lithium cobalt oxide lithium ion battery in the plant protection unmanned aerial vehicle.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a ternary high-rate polymer lithium ion battery and a manufacturing method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a ternary high-rate polymer lithium ion battery comprises a closed soft package, wherein a positive tab and a negative tab are arranged on the surface of the soft package, electrolyte is filled in the soft package, a plurality of layers of positive plates and negative plates are laid, the positive plates and the negative plates are sequentially laminated at intervals, diaphragms are laid between adjacent positive plates and negative plates for separation, all the positive plates and the positive tabs are connected in parallel through ultrasonic welding, and all the negative plates and the negative tabs are connected in parallel through ultrasonic welding;
the positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer comprises the following components in percentage by mass: 90-94% of positive active material, 2-4% of conductive agent, 4-6% of adhesive,
the negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer comprises the following components in percentage by mass: 91-95% of negative electrode active material, 1.2-2.5% of conductive agent, 3.5-6% of adhesive and 0.3-0.5% of oxalic acid.
Further, the positive electrode active material is a ternary 111 material, the positive electrode conductive agent comprises conductive carbon black and a single-walled carbon nanotube, the negative electrode active material is a secondary crushed carbon microsphere, the negative electrode conductive agent comprises conductive carbon black and a single-walled carbon nanotube, and the adhesive is PVDF.
Further, the anodal mass flow body is 10um-16 um's two-sided light aluminium foil, the negative pole fluid is 6um-9 um's two-sided light copper foil.
Furthermore, the diaphragm adopts a single-layer polypropylene film, the air permeability is 125-275sec/100cc, and the thickness is 23-27 um.
Further, the electrolyte comprises a solute, a solvent and an additive, wherein the solute is LiP6, the concentration is 1.4mol/L, the volume ratio of the solvent is EC/DMC (1/2.5), and the additive is PS and PST.
Further, the surface density of the anode slurry coated on the surface of the anode current collector is 270-290 g/square meter, and the compaction density of rolling after the anode slurry layer is coated is 3.25-3.35 g/m3The surface density of the negative electrode slurry coated on the surface of the negative electrode current collector is 155 g/square meter together with 145 g/square meter, and the compaction density of rolling after the negative electrode slurry layer is coated is 1.55-1.65g/m3And the heating temperature of the negative electrode pressing roller is 120-150 ℃.
Further, the ternary 111 material has a specific surface area of 0.8-1m2/g, D50 is 8um-13um, the specific surface area of the secondary crushing carbon microsphere is 1.5-2 square meters per gram, and D50 is 8-13 um.
Furthermore, the mass ratio of the conductive carbon black of the positive electrode of the battery to the single-walled carbon nanotube is 2/(0.5-1), and the mass ratio of the conductive carbon black of the negative electrode to the single-walled carbon nanotube is 1/(0.5-1).
A method for manufacturing a ternary high-rate polymer lithium ion battery comprises the following steps:
the method comprises the following steps: manufacturing a positive plate: uniformly stirring a ternary 111 material, conductive carbon black, a single-walled carbon nanotube and a PVDF adhesive in proportion, adding NMP to prepare a positive electrode slurry, coating the positive electrode slurry on the surface of a double-sided polished aluminum foil, and sequentially drying, rolling and die-cutting to prepare a sheet to obtain a positive plate containing a tab;
step two: manufacturing a negative plate: uniformly stirring the secondary crushed carbon microspheres, the conductive carbon black, the single-walled carbon nanotubes and the PVDF adhesive in proportion, adding NMP to prepare a negative electrode slurry, coating the negative electrode slurry on the surface of a double-sided smooth copper foil, and sequentially drying, rolling at high temperature and die-cutting to prepare a negative electrode sheet containing a tab;
step three: assembling the battery: sequentially laminating the negative plate and the positive plate, clamping a diaphragm between the adjacent positive plate and the negative plate, fixing the laminated negative plate, diaphragm and positive plate in a shell through a support, extending a positive lug and a negative lug out of the open end of the shell, injecting electrolyte into the shell, and packaging the shell;
step four: formation and grading of the battery: the assembled battery is charged to 4.2V cut-off according to the current of 0.5C, and is aged for 7 days at 40 ℃, the capacity grading discharge cut-off voltage of the battery is 2.7V, and the charge cut-off voltage is 4.2V.
Has the advantages that:
compared with the traditional lithium cobalt oxide lithium ion battery, the lithium cobalt oxide lithium ion battery adopts the ternary material as the anode material, reduces the impedance value, improves the conductivity and the capacity, and has the advantages of good rate capability, good cycle performance and good safety while reducing the material cost.
Drawings
FIG. 1 is a 10C discharge diagram of the present invention,
figure 2 is a schematic of the 1C cycle life of the present invention,
wherein, A is the 10C multiplying power discharge curve chart in the embodiment 2, B is the 10C multiplying power discharge curve chart in the embodiment 1, C is the 1C cycle life curve chart in the embodiment 2, and D is the 1C cycle life curve chart in the embodiment 1.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
Ternary high-rate polymer lithium ion battery, including positive plate, negative pole piece and plastic-aluminum membrane shell, positive plate and negative pole piece are range upon range of, lay the negative pole piece earlier, be provided with the diaphragm between adjacent positive plate and the negative pole piece, positive plate and negative pole piece range upon range of good are placed in the plastic-aluminum membrane shell, be provided with electrolyte in the plastic-aluminum membrane shell, positive plate includes anodal mass flow body and the anodal thick liquids of coating on anodal mass flow body surface, all positive plate and anodal ear are parallelly connected through ultrasonic bonding, each composition and the percentage of its shared gross mass are in the anodal thick liquids: 90% -94% of positive active material, 2% -4% of conductive agent and 4% -6% of adhesive, wherein the negative plate comprises a negative current collector and negative slurry coated on the surface of the negative current collector, all the negative plates and the negative lugs are connected in parallel by ultrasonic welding, and the negative slurry comprises the following components in percentage by mass: 91-95% of negative electrode active material, 1-2% of conductive agent, 4-6% of adhesive and 0.3-0.5% of oxalic acid.
A method for manufacturing a ternary high-rate polymer lithium ion battery, embodiment 1:
a. manufacturing a positive plate: uniformly stirring a ternary 111 material, conductive carbon black, a single-walled carbon nanotube and PVDF according to a mass ratio of 93.5:2:0.5:4, adding NMP to prepare a positive electrode slurry, coating the positive electrode slurry on an aluminum foil, and sequentially drying, rolling and die-cutting to prepare a pole piece containing 1 pole lug, wherein the density of the double-coated surface of the positive electrode piece is 280g/m during coating2The compaction density of the positive plate is 3.25g/cm during rolling3。
b. The preparation method of the negative plate comprises the steps of uniformly mixing the secondary crushed carbon microspheres, the conductive carbon black, the PVDF and the oxalic acid according to the mass ratio of 93.7:2:4:0.3, adding NMP to prepare negative slurry, and coating the negative slurryTo on the copper foil, through drying, high temperature roll-in proper order, the cross cutting film-making obtains the negative pole piece that contains 1 utmost point ear, and during wherein the coating, the two-sided surface density of negative pole piece is: 150 g/m2The compacted density of the negative plate is 1.55g/cm3。
c. Assembling the battery: and (3) matching 25um single-layer polypropylene dry-process diaphragm with air permeability of 220sec/100ml with the positive plate and the negative plate of the battery, laminating, wherein the first plate is the negative plate, and finally injecting the electrolyte with the ratio to assemble the soft package battery.
d. Formation and grading of the battery: the cell was charged to a 4.2V cutoff at 0.5C and aged at 40℃ for 7 days. The capacity grading discharge cut-off voltage of the battery is 2.7V, and the charge cut-off voltage is 4.2V.
Example 2:
a. manufacturing a positive plate: uniformly stirring a ternary 111 material, conductive carbon black, a single-walled carbon nanotube and PVDF according to a mass ratio of 94:2:0.5:3.5, adding NMP to prepare a positive electrode slurry, coating the positive electrode slurry on an aluminum foil, and sequentially drying, rolling and die-cutting to prepare a pole piece containing 1 pole lug, wherein the density of the double-coated surface of the positive electrode piece is 270g/m during coating2The compaction density of the positive plate is 3.30g/cm during rolling3。
b. And (3) manufacturing a negative plate: uniformly mixing the mesocarbon microbeads, the conductive carbon black, the PVDF and the oxalic acid according to a mass ratio of 93.7:1:5:0.3, adding NMP to prepare a negative electrode slurry, coating the negative electrode slurry on copper foil, drying, rolling at high temperature, and performing die cutting to prepare a negative electrode sheet containing 1 tab, wherein during coating, the density of the two surfaces of the negative electrode sheet is as follows: 145g/m2The compacted density of the negative pole piece is 1.60g/cm3。
c. Assembling the battery: and (3) matching 25um PP dry-method diaphragm with air permeability of 220sec/100ml with the positive plate and the negative plate of the battery, laminating, taking the first plate as the negative electrode, and finally injecting the electrolyte with the ratio to assemble the soft package battery.
d. Formation and grading of the battery: the cell was charged to a 4.2V cutoff at 0.5C and aged at 40℃ for 7 days. The capacity grading discharge cut-off voltage of the battery is 2.7V, and the charge cut-off voltage is 4.2V.
Compared with the traditional lithium cobalt oxide lithium ion battery, the lithium cobalt oxide lithium ion battery adopts the ternary material as the anode material, reduces the impedance value, improves the conductivity and the capacity, and has the advantages of good rate capability, good cycle performance and good safety while reducing the material cost.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. A ternary high-rate polymer lithium ion battery is characterized in that: the soft package comprises a closed soft package, wherein positive lugs and negative lugs are arranged on the surface of the soft package, electrolyte is filled in the soft package, a plurality of layers of positive plates and negative plates are laid, the positive plates and the negative plates are sequentially laminated at intervals, diaphragms are laid between adjacent positive plates and negative plates for separation, all the positive plates and the positive lugs are connected in parallel through ultrasonic welding, and all the negative plates and the negative lugs are connected in parallel through ultrasonic welding;
the positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer comprises the following components in percentage by mass: 90-94% of positive active material, 2-4% of conductive agent, 4-6% of adhesive,
the negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer comprises the following components in percentage by mass: 91-95% of negative electrode active material, 1.2-2.5% of conductive agent, 3.5-6% of adhesive and 0.3-0.5% of oxalic acid.
2. The ternary high-rate polymer lithium ion battery according to claim 1, wherein: the anode active material is a ternary 111 material, the anode conductive agent comprises conductive carbon black and a single-walled carbon nanotube, the cathode active material is a secondary crushed carbon microsphere, the cathode conductive agent comprises conductive carbon black and a single-walled carbon nanotube, and the adhesive is PVDF.
3. The ternary high-rate polymer lithium ion battery according to claim 1, wherein: the anodal mass flow body is 10um-16 um's two-sided light aluminium foil, the negative pole fluid is 6um-9 um's two-sided light copper foil.
4. The ternary high-rate polymer lithium ion battery according to claim 1, wherein: the diaphragm adopts a single-layer polypropylene film, the air permeability is 125-275sec/100cc, and the thickness is 23-27 um.
5. The ternary high-rate polymer lithium ion battery according to claim 1, wherein: the electrolyte comprises a solute, a solvent and an additive, wherein the solute is LiP6, the concentration is 1.4mol/L, the volume ratio of the solvent is EC/DMC (1/2.5), and the additive is PS and PST.
6. The ternary high-rate polymer lithium ion battery according to claim 1, wherein: the surface density of the positive slurry layer coated on the surface of the positive current collector is 270 plus 290 g/square meter, and the compaction density of rolling after the positive slurry layer is coated is 3.25-3.35 g/m3The negative electrode slurry layer is coated on the negative electrodeThe surface density of the current collector is 145-155 g/square meter, and the compaction density of the negative slurry layer after coating is 1.55-1.65g/m3And the heating temperature of the negative electrode pressing roller is 120-150 ℃.
7. The ternary high-rate polymer lithium ion battery according to claim 2, wherein: the specific surface area of the ternary 111 material is 0.8-1m2/g, D50 is 8um-13um, the specific surface area of the secondary crushing carbon microsphere is 1.5-2 square meters per gram, and D50 is 8-13 um.
8. The ternary high-rate polymer lithium ion battery according to claim 2, wherein: the mass ratio of the conductive carbon black of the positive electrode of the battery to the single-walled carbon nanotube is 2/(0.5-1), and the mass ratio of the conductive carbon black of the negative electrode to the single-walled carbon nanotube is 1/(0.5-1).
9. A method for manufacturing a ternary high-rate polymer lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: manufacturing a positive plate: uniformly stirring a ternary 111 material, conductive carbon black, a single-walled carbon nanotube and a PVDF adhesive in proportion, adding NMP to prepare a positive electrode slurry, coating the positive electrode slurry on the surface of a double-sided polished aluminum foil, and sequentially drying, rolling and die-cutting to prepare a sheet to obtain a positive plate containing a tab;
step two: manufacturing a negative plate: uniformly stirring the secondary crushed carbon microspheres, the conductive carbon black, the single-walled carbon nanotubes and the PVDF adhesive in proportion, adding NMP to prepare a negative electrode slurry, coating the negative electrode slurry on the surface of a double-sided smooth copper foil, and sequentially drying, rolling at high temperature and die-cutting to prepare a negative electrode sheet containing a tab;
step three: assembling the battery: sequentially laminating the negative plate and the positive plate, clamping a diaphragm between the adjacent positive plate and the negative plate, fixing the laminated negative plate, diaphragm and positive plate in a shell through a support, extending a positive lug and a negative lug out of the open end of the shell, injecting electrolyte into the shell, and packaging the shell;
step four: formation and grading of the battery: the assembled battery is charged to 4.2V cut-off according to the current of 0.5C, and is aged for 7 days at 40 ℃, the capacity grading discharge cut-off voltage of the battery is 2.7V, and the charge cut-off voltage is 4.2V.
CN201911059026.2A 2019-11-01 2019-11-01 Ternary high-rate polymer lithium ion battery and manufacturing method thereof Withdrawn CN111063880A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112151755A (en) * 2020-09-08 2020-12-29 江苏塔菲尔新能源科技股份有限公司 Positive plate and battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112151755A (en) * 2020-09-08 2020-12-29 江苏塔菲尔新能源科技股份有限公司 Positive plate and battery

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