CN113451541B - High-voltage lithium ion positive electrode piece, battery and manufacturing method thereof - Google Patents

High-voltage lithium ion positive electrode piece, battery and manufacturing method thereof Download PDF

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CN113451541B
CN113451541B CN202110594165.6A CN202110594165A CN113451541B CN 113451541 B CN113451541 B CN 113451541B CN 202110594165 A CN202110594165 A CN 202110594165A CN 113451541 B CN113451541 B CN 113451541B
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positive electrode
conductive
polymer binder
current collector
fluorinated
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CN113451541A (en
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罗英
闵凡奇
丁赵波
解晶莹
晏莉琴
黄嘉烨
郭瑞
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Shanghai Aerospace Power Technology Co Ltd
Shanghai Institute of Space Power Sources
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Shanghai Power Energy Storage Battery System Engineering Technology Co ltd
Shanghai Institute of Space Power Sources
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    • 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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
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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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 provides a high-voltage lithium ion positive electrode plate, a battery and a manufacturing method thereof, wherein the positive electrode plate comprises a composite current collector and positive electrode slurry coated on the surface of the current collector, the composite current collector comprises an aluminum base material with concave holes on the surface, and a first corrosion inhibition conducting layer and a second conducting layer which are respectively coated on two surfaces of the aluminum base material, the first corrosion inhibition conducting layer is formed by blending a corrosion inhibitor and a conducting polymer, and the second conducting layer comprises a polymer binder I carrying guest molecules, a polymer binder and conducting carbon. In addition, the invention also provides a preparation method of the high-voltage lithium ion battery. The positive electrode plate and the battery preparation method provided by the invention improve the adhesion between the surface of the current collector and the active material, and improve the contact adhesion between the current collector and the positive active material under a high-voltage condition, thereby improving the electrochemical performance of the high-voltage lithium ion battery.

Description

High-voltage lithium ion positive electrode piece, battery and manufacturing method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium ion positive electrode, a battery and a manufacturing method of the high-voltage lithium ion positive electrode and the battery.
Background
The main direction of development of lithium ion batteries is high energy density, high power and high safety. One way to increase the energy density of a battery is to increase the operating voltage of the battery. Currently, the research researchers are interested in new lithium ion battery materials with working potential close to 5V, such as spinel-type manganese-based materials and olivine-type phosphate materials, which have relatively stable crystal structure and working potential greater than 4.5V, and are beneficial to maintaining structural and performance stability in the circulation process. However, high voltage lithium ion batteries face a number of problems in their application. Such as decomposition of the electrolyte at high voltage, severe side reactions at high temperature, etc., which are mainly improved from the viewpoint of the electrolyte. By improving the oxidation potential of the electrolyte or optimizing the formation method of the battery, a stable and uniform electrode/electrolyte interface layer is constructed, and the electrochemical problem of the high-voltage lithium ion battery is improved. CN202010043273.X discloses a high-voltage lithium ion battery electrolyte additive, an electrolyte, a battery and a formation method thereof, wherein the additive of pyridine compounds is sufficiently decomposed by formation at high temperature and high voltage, and a stable interface film containing LixNOY is formed on the surfaces of a positive electrode and a negative electrode, so that the efficiency and the cycle performance of the battery are improved. However, dissolution and re-deposition of interfacial film compositions at high temperatures by charge-discharge formation are easily induced, and co-intercalation of solvent molecules is exacerbated, giving new films with porous structures and limited improvement in high voltage battery performance. In addition to the above problems, in the lithium ion battery, the separator and the inactive materials, such as the current collector, the conductive agent, the binder, etc., play an important role in constructing a good conductive network and ensuring normal diffusion of lithium ions. The stability of these battery modules at high voltages is also highly challenging and not negligible. CN201810697572.8 proposes to adopt SWCNT/MWCNT composite conductive agent on the basis of selection of high-voltage single crystal positive electrode material, and compared with pure MWCNT conductive agent, the SWCNT/MWCNT composite conductive agent can effectively improve the cycle performance and rate performance of a battery cell under high voltage, but the patent content mainly improves the performance of a high-voltage battery system with working voltage below 4.5V.
In the lithium ion battery, the current collector mainly provides an electronic channel for electrochemical reaction, thereby accelerating charge transfer, reducing electrochemical polarization, improving coulombic efficiency of the battery in the charging and discharging processes, and not participating in Li + The de-intercalation reaction of (1). For the positive electrode of a lithium ion battery, aluminum metal is generally used as a current collector. Although the standard electrode potential of metallic aluminum is lower than the working potential of the lithium ion battery, the standard electrode potential is only 1.39V (vs + ) However, a layer of dense passivation film, mainly aluminum oxide, is formed on the surface of the aluminum current collector, so that the current collector is prevented from being oxidized in a certain charging and discharging voltage interval. For LiPF 6 Electrolyte system, it is generally accepted that decomposition products of the electrolyte and Al 3+ Combine to form stable AlF 3 And organic aluminum salt is covered on the surface of the current collector. This has a positive effect on inhibiting corrosion of the aluminum current collector. Currently, in a lithium ion battery system using an aluminum current collector, the upper limit voltage for charging the battery is mainly concentrated around 4.2V. For oxidation potential>In a 4.5V high voltage lithium ion battery system, the high operating voltage poses a serious challenge to the stability of the aluminum current collector. Once the current collector is corroded, the contact between the active substance and the current collector is reduced, so that the active substance and the current collector are stripped, the resistance of the battery is increased by products generated by corrosion, and the formed soluble products are dissolved in the electrolyte, so that the self-discharge rate of the battery is increased. In severe cases, soluble products migrate to the negative electrode and undergo reductive deposition. Both of these conditions cause a decline in battery capacity. The CN201410637410.7 patent discloses a composite current collector with high corrosion resistance and high conductivity and a manufacturing method thereof. The composite current collector comprises a substrate and conductive adhesive coated on the surface of the substrateA transition layer and a conductive anticorrosive layer. Although the method improves the corrosion resistance and the conductivity of the current collector, the conductive anticorrosion slurry is coated on the base material coated with the conductive adhesive transition layer by adopting a transfer coating, blade coating or extrusion coating mode, the coating thickness reaches 0.1-1 mm, and the thicker coating thickness increases the weight of the current collector, thereby being not beneficial to improving the energy density of a battery.
The lithium ion battery current collector disclosed in CN 111463436A comprises a three-layer composite structure, which is: the current collector comprises a current collector base material layer, a corrosion-resistant oxide layer sputtered on the current collector base material layer and a conductive polymer layer grown in situ on the surface of the corrosion-resistant oxide layer. Since organic electrolyte is generally used in lithium ion batteries, the electrolyte is acidic, and the oxide layer in the current collector is still likely to be corroded in an acidic environment for a long time.
Therefore, it is very necessary to provide a method for preparing a battery having a high voltage without affecting other performances of the battery.
Disclosure of Invention
Aiming at the technical defects in the prior art, the invention discloses a high-voltage lithium ion positive electrode piece, a battery and a manufacturing method thereof.
The high-voltage positive electrode plate comprises a composite current collector and positive electrode slurry coated on the surface of the current collector. A first corrosion inhibition conducting layer with thin and uniform nano-scale thickness is constructed on the surface of the current collector by utilizing a molecule self-assembly method, and the overall thickness of the current collector is effectively reduced on the premise of ensuring the inhibition of the corrosion of the current collector. Meanwhile, by introducing a high-molecular functional chain with a host-guest self-repairing function into the polymer binders in the second conductive layer and the positive electrode slurry respectively, the contact adhesion between the current collector and the positive active material under a high-voltage condition is improved by utilizing a molecular recognition effect. In addition, by providing a formation method of low SOC, high voltage and high temperature shelving and low temperature and low current charging, the film forming stability and compactness of the perfluorinated organic electrolyte on the surface of the electrode are improved, and the battery performance is improved.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the invention relates to a high voltage lithium ion positive electrode plate, which comprises a composite current collector and positive electrode slurry coated on the surface of the current collector; the composite current collector comprises a composite aluminum current collector; the composite aluminum current collector comprises an aluminum substrate with concave holes on the surface, and a first corrosion inhibition conducting layer and a second conducting layer which are respectively coated on two sides of the aluminum substrate; the first corrosion inhibition conducting layer is formed by blending a corrosion inhibitor and a conducting polymer; the HOMO value of the conductive polymer is less than-11 eV; the second conducting layer comprises a polymer binder I for carrying guest molecules, a polymer binder and conductive carbon which are blended; the HOMO value of the polymer binder I carrying the guest molecules is less than-11 eV.
The HOMO value of the conducting polymer is selected to be smaller than-11 eV, because the lower the HOMO value of the material is, the higher the oxidation potential is, and the problem that the current collector is easy to corrode under high potential is solved by selecting the polymer material with high oxidation potential; the HOMO value of the polymer binder I carrying the guest molecules is selected to be smaller than-11 eV because the HOMO value of the material is higher, and the problem that a current collector is easy to corrode at a high potential is solved by selecting the polymer material with the high oxidation potential.
As an embodiment of the present invention, the positive electrode slurry comprises a positive electrode active material having an oxidation potential of greater than 4.5V (vs. Li/Li +), a positive electrode conductive agent, a polymer binder, and a host molecule-carrying polymer binder ii; the HOMO value of the polymer binder II carrying the host molecules is less than-11 eV; the positive electricity active material is one or more of lithium nickel manganese oxide, lithium iron manganese oxide, lithium cobalt phosphate and lithium nickel phosphate with olivine structures and lithium nickel vanadate with inverse spinel structures.
As an embodiment of the invention, the corrosion inhibitor is selected from one or more of fluorinated ethylene-vinyl acetate resin, fluorinated polyacrylic resin, fluorinated polystyrene resin, fluorinated acrylate and fluorinated phosphate; the conductive polymer is one or more of conductive fluorinated polypyrrole and conductive fluorinated polyurethane.
As an embodiment of the invention, the polymeric binder is selected from one or more of polyvinylidene fluoride, fluorinated epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene; the guest molecules in the guest molecule-carrying polymer binder I are adamantane, and the polymer binder is selected from one or more of polyvinylidene fluoride, fluorinated epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene; the main molecules of the polymer binder II carrying the main molecules are cyclodextrin, and the polymer binder is selected from one or more of polyvinylidene fluoride, fluorinated epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene.
As an embodiment of the invention, the thickness of the first corrosion-inhibition conducting layer is 10nm to 100nm; the mass ratio of the corrosion inhibitor to the conductive polymer is 1:3-1:1; the thickness of the second conducting layer is 0.1-10 μm; the mass ratio of the polymer binder I for carrying the guest molecules, the polymer binder and the conductive carbon is 1.
The mass ratio of the corrosion inhibitor to the conductive polymer is 1:3-1:1, if the mass ratio of the corrosion inhibitor to the conductive polymer is less than 1:3, the content of the corrosion inhibitor is too low, so that the corrosion resistance of the surface of the current collector is reduced; if the mass ratio of the corrosion inhibitor to the conductive polymer is greater than 1:1, the conductivity of the surface of the current collector is reduced due to the excessively low content of the conductive polymer.
The invention also selects a polymer binder I for carrying guest molecules, a polymer binder and conductive carbon to be blended according to the mass ratio of 1; if the mass ratio of the polymer binder I carrying the guest molecules to the polymer binder and the conductive carbon is less than 1; if the mass ratio of the polymer binder I carrying the guest molecules to the polymer binder and the conductive carbon is more than 1.
On the other hand, the invention relates to the application of a high-voltage lithium ion positive electrode plate in the preparation of a battery, and the preparation method of the battery comprises the following steps:
s1: manufacturing a composite aluminum current collector: dissolving a corrosion inhibitor and a conductive polymer by using a solvent at 50-120 ℃ in an inert atmosphere to form a corrosion inhibition conductive solution; immersing the aluminum substrate with concave holes on the surface into a corrosion inhibition conductive solution, standing for 3-10 h, and evaporating the corrosion inhibition conductive solution to dryness at 60-150 ℃ to obtain an aluminum current collector coated with a first corrosion inhibition conductive layer; mixing the polymer binder I, the polymer binder, the conductive carbon material and a solvent to form conductive slurry, and adjusting the viscosity of the slurry to 1000-6000 mPa.S according to the using amount of the solvent; coating or screen printing the slurry on the surface of the first corrosion inhibition conducting layer of the aluminum current collector, and drying;
s2: manufacturing a positive electrode: dissolving a polymer binder and a polymer binder II in NMP under a low dew point environment to ensure that the total concentration of the polymer binder and the polymer binder II carrying the main body molecules is 1-8%; adding a positive electrode conductive agent, stirring at a high speed, adding a positive electrode active material, and continuously stirring at a high speed to form positive electrode slurry; coating the electrode slurry on a positive current collector, and after drying a solvent, rolling and punching the formed electrode to prepare a positive electrode;
s3: preparing a prelithiation negative electrode: dissolving a negative electrode binder in NMP under a low dew point environment to ensure that the concentration of the negative electrode binder is 1-10%; adding a conductive agent and stirring at a high speed; adding a negative electrode active material, and continuously stirring to form negative electrode slurry; coating the electrode slurry on a negative current collector, drying a solvent, and rolling and punching the formed electrode to prepare a negative electrode; soaking lithium foil in organic electrolyte, rolling to the surface of negative electrode,
laying aside;
s4: manufacturing a high-voltage lithium ion battery: under the low dew point environment, the prepared positive electrode, prelithiation negative electrode and diaphragm are laminated or coiled to prepare a dry cell, the tabs are welded and then packaged by an aluminum plastic film, and organic electrolyte is injected into the dry cell and then is pre-vacuumized to prepare a high-voltage lithium ion battery;
s5: formation of a battery: fixing the prepared high-voltage lithium ion battery tab, charging for 2-4 h at a rate of 0.02-0.5C under the condition of normal temperature, then standing in a drying oven at 40-55 ℃ for 10-24 h, and then charging to a cut-off potential at a low temperature of-10 ℃ and a constant current at a rate of 0.02-0.5C; and (5) secondary vacuum-pumping of the battery.
In step S1, the mass ratio of the sum of the mass of the corrosion inhibitor and the conductive polymer to the mass of the solvent is 1:2 to 1:5; the solvent is selected from one of strong polar organic solvents such as tetrahydrofuran, amyl acetate, dimethyl sulfoxide and the like; the volume ratio of the corrosion inhibition conductive solution to the aluminum substrate is 2:1-20.
The mass ratio of the sum of the mass of the corrosion inhibitor and the conductive polymer to the mass of the solvent is 1:5-1:2, and if the ratio is less than 1:5, the solution concentration is too low, so that the compactness of the first corrosion inhibition conductive layer is reduced; if the ratio is greater than 1:2, the dispersion uniformity of the corrosion inhibitor and the conductive polymer on the surface of the current collector is reduced due to the excessively high concentrations of the corrosion inhibitor and the conductive polymer.
In step S2, the positive electrode active material accounts for 80% to 96% by mass of the positive electrode slurry, the positive electrode conductive agent accounts for 2% to 10% by mass of the positive electrode slurry, the polymer binder II carrying the host molecule accounts for 1% to 5% by mass of the positive electrode slurry, and the polymer binder accounts for 1% to 5% by mass of the positive electrode slurry; the positive electrode conductive agent is a combined conductive agent and comprises a granular conductive agent, a linear conductive agent and a sheet conductive agent, wherein the percentage content of the granular conductive agent is 0-40%, the granular conductive agent is one or more of super carbon black, conductive carbon black, ks-6 and Ks-15, the linear conductive agent is one or more of VGCF and carbon nano tubes, and the sheet conductive agent is graphene.
The percentage content of the granular conductive agent is limited to 0-40%, and if the percentage content of the granular conductive agent is higher than 40%, a large amount of the granular conductive agent can be used as a place for decomposing the electrolyte due to the catalytic action.
As an embodiment of the present invention, in step S3, the negative electrode active material is present in a mass percentage of the positive electrode slurryIs graphite material, the proportion of the negative electrode active material is 90-98 percent; the negative electrode conductive agent is selected from one or more of super carbon black, conductive carbon black, ks-6 and Ks-15, and the proportion of the negative electrode conductive agent is 1-5%; the negative electrode binder is selected from one or more of polyvinylidene fluoride, fluorinated epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene, and the proportion of the negative electrode binder is 1-5%; the organic electrolyte is a perfluorinated organic electrolyte, wherein the solvent is selected from any three or more of FEC, FEMC, HFE, FDMC and TFEC, but at least comprises HFE and FEMC, the solute is a mixed lithium salt, and comprises any two or more of lithium hexafluorophosphate, liODFB and LiBOB, but at least comprises LiODFB; the oxidation potential of the organic electrolyte is more than 5V, and the conductivity is more than 5.5S/cm 2 。
As an embodiment of the present invention, the separator in step S4 is a coated separator, the separator substrate is PE or PP, and the coating is PVDF or a metal oxide; the thickness of the diaphragm is 5 nm-200 nm; the organic electrolyte solution contains FEMC 50-70 vol%, HFE 10-40 vol%, and solute LiODFB 1-10 mol%.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a molecular self-assembly method on the surface of a concave hole aluminum current collector with a large specific surface area, utilizes the bonding effect of Al-O, al-O, al-C and other bonds on the surface of the aluminum current collector and organic molecules to realize the deposition of a corrosion inhibition layer with conductivity on the surface of the aluminum current collector to form a thin and uniform corrosion inhibition conducting layer, the thickness of the corrosion inhibition conducting layer is only nano-scale, and the overall thickness of the current collector is reduced on the premise of ensuring the corrosion inhibition of the current collector.
(2) According to the invention, a polymer functional chain with a host-guest self-repairing function is introduced into the second conducting layer on the surface of the current collector and the polymer binder in the anode slurry, and the molecular recognition function between host-guest molecules is utilized, so that the adhesion between the surface of the current collector and an active material is improved, the contact adhesion between the current collector and the active material under a high-voltage condition is improved, and the electrochemical performance of the high-voltage lithium ion battery is improved.
(3) According to the invention, the first corrosion inhibition conducting layer and the second conducting layer are designed on the surface of the current collector, and the high conductivity of the carbonaceous particles is utilized to transfer the electron exchange reaction between the electrolyte and the aluminum to the carbonaceous particles, so that the stability of the aluminum foil under high voltage is improved. Meanwhile, the contact area between the positive electrode and the current collector is increased, the contact impedance between the active substance and the current collector is reduced, and the decomposition of a large amount of electrolyte under a high polarization potential is relieved, so that the electrochemical performance of the high-voltage lithium ion battery is improved.
(4) The invention also improves the film forming stability and compactness of the perfluorinated organic electrolyte on the surface of the electrode by adopting a formation system of high-temperature shelving at low SOC and high voltage and low-temperature small-current charging in the formation process of the battery and utilizing the characteristics of promoting the decomposition of the electrolyte at high temperature and improving the compactness and low resistance of an interface film at low temperature, thereby improving the interface of the electrode and improving the circulation stability of the battery.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a schematic diagram of a high-voltage lithium ion positive electrode according to embodiments 1 to 6 of the present invention, where 1-1 is an upper positive electrode slurry layer, 1-2 is a lower positive electrode slurry layer, 2-1 is an upper second conductive layer, 2-2 is a lower second conductive layer, 3 is a metal current collector, 4-1 is an upper first corrosion-inhibiting conductive layer, and 4-2 is a lower first corrosion-inhibiting conductive layer.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
Example 1
The preparation method of the polymer lithium ion battery related to the embodiment is as follows:
(1) Manufacturing a composite aluminum current collector: under inert atmosphere, weighing the fluorinated ethylene-vinyl acetate resin and the conductive fluorinated polyurethane according to a 1:2 mass ratio, weighing a tetrahydrofuran solvent according to 5 times of the sum of the mass of the fluorinated ethylene-vinyl acetate resin and the mass of the conductive fluorinated polyurethane, and dissolving the fluorinated ethylene-vinyl acetate resin and the conductive fluorinated polyurethane in the tetrahydrofuran solvent at 80 ℃ to form the corrosion inhibition conductive solution. Wherein the HOMO value of the conductive fluorinated polyurethane is-11.3 eV. Taking an aluminum substrate with a certain volume and concave holes on the surface according to 8 times of the volume of the corrosion inhibition conductive solution, immersing the aluminum substrate into the corrosion inhibition conductive solution, and standing for 5 hours. And evaporating the solution to dryness at 100 ℃ to obtain the aluminum current collector coated with the first corrosion inhibition conducting layer. Weighing polyvinylidene fluoride carrying adamantane molecular chains, polyvinylidene fluoride and graphite materials according to the mass ratio of 1. Preparing uniform conductive slurry under high-speed shearing force, adjusting the viscosity of the slurry to 3000 mPa.S, and covering the slurry on the surface of the first corrosion inhibition conductive layer of the aluminum current collector by a coating method to form the composite aluminum current collector comprising the first corrosion inhibition conductive layer and the second conductive layer.
(2) Manufacturing a positive electrode: under a low dew point environment, weighing polyvinylidene fluoride, polyvinylidene fluoride carrying cyclodextrin molecular chains, a conductive agent and a spinel type lithium nickel manganese oxide material according to a mass ratio of 1.25 to 1.25. Wherein the conductive agent comprises a mixture of super carbon black, VGCF and graphene, and the ratio is 35. The HOMO value of the polyvinylidene fluoride carrying cyclodextrin molecular chains is-12.0 eV. Dissolving the two weighed binders in NMP, adding the weighed mixture of the conductive agents, stirring at a high speed for a certain time, adding the weighed lithium nickel manganese oxide material, and stirring at a high speed for a certain time to form uniformly dispersed lithium nickel manganese oxide electrode slurry. And coating the slurry on a composite aluminum current collector, drying the solvent, and rolling and punching the formed electrode to prepare a positive electrode.
(3) Preparing a prelithiation negative electrode: under a low dew point environment, weighing polyvinylidene fluoride, super carbon black and the mesocarbon microbead anode material according to the mass ratio of 1.5. Dissolving weighed polyvinylidene fluoride in NMP, adding weighed super carbon black, stirring at a high speed for a certain time, adding weighed mesocarbon microbead material, and stirring at a high speed for a certain time to form uniformly dispersed negative electrode slurry. And coating the slurry on a negative current collector, drying the solvent, and rolling and punching the formed electrode to prepare a negative electrode. And infiltrating a lithium foil with the thickness of 1 mu m into the organic electrolyte, rolling the lithium foil onto the surface of the negative electrode, and standing for 5 hours to form a pre-lithiated negative electrode.
(4) Manufacturing a high-voltage lithium ion battery: and in a low dew point environment, preparing a dry battery cell by laminating the prepared positive electrode and negative electrode and the PE diaphragm with the PVDF coating, welding the tabs, packaging by adopting an aluminum plastic film, injecting a perfluorinated organic electrolyte into the dry battery cell, and pre-vacuumizing to prepare the high-voltage lithium ion battery. The solvent of the perfluorinated organic electrolyte is FEC, FEMC and HFE, the solvent ratio is 2. The oxidation potential of the electrolyte was 5.3V, and the conductivity was 6.5S/cm 2 。
(5) Formation of a battery: the prepared high-voltage lithium nickel manganese oxide lithium ion battery tab is fixed on a charge-discharge tester to be charged for 2h at a rate of 0.05C under the normal temperature condition, then is placed in a baking oven at the temperature of 45 ℃ for 10h, and is charged to be charged to 4.9V at a constant current at a low temperature of 0.05C. And carrying out secondary vacuum pumping on the battery to obtain the high-voltage lithium nickel manganese oxide lithium ion battery.
The formed battery is subjected to charge-discharge cycle tests at normal temperature of 25 ℃ and high temperature of 55 ℃ at 0.2C and 1C respectively.
Example 2
In this example, a high voltage lithium nickel manganese oxide lithium ion battery was prepared according to substantially the same method and conditions as in example 1. The difference is that in this embodiment: the first corrosion inhibition conducting layer of the composite aluminum current collector comprises fluorinated polyacrylic resin and conductive fluorinated polypyrrole, wherein the mass ratio of the fluorinated polyacrylic resin to the conductive fluorinated polypyrrole is 1:1. The HOMO value of the electrically conductive fluorinated polypyrrole was-11.9 eV. The second conductive layer includes polyvinylidene fluoride carrying adamantane molecular chains, polyvinylidene fluoride, and a carbon nanotube material. The conductive agent in the positive electrode comprises a mixture of super carbon black, carbon nanotubes and graphene in a ratio of 30. The formation condition of the battery is charging for 3h at 0.05C rate under the normal temperature condition, then standing in a 50 ℃ oven for 10h, and then charging to 4.9V at 0.05C rate under the low temperature condition of 10 ℃ and constant current.
Example 3
In this example, a high-voltage cobalt phosphate lithium ion battery was prepared in substantially the same manner and under substantially the same conditions as in example 1. The difference is that in this embodiment: the second conductive layer in the composite aluminum current collector comprises fluorinated epoxy resin carrying adamantane molecular chains, fluorinated epoxy resin and a carbon nanotube material. The HOMO value of the fluorinated epoxy resin having an adamantane molecular chain carried thereon was-12.5 eV. The positive electricity active material in the positive electrode adopts lithium cobalt phosphate, and the binder is fluorinated epoxy resin and fluorinated epoxy resin carrying cyclodextrin molecular chains. The HOMO value of the fluorinated epoxy resin carrying cyclodextrin molecular chains is-12.7 eV. The conductive agent comprises a mixture of Ks-6, VGCF and graphene in a ratio of 35. The formation condition of the battery is charging for 2h at 0.05C rate under the normal temperature condition, then standing in a 50 ℃ oven for 10h, and then charging to 5V at 0.05C rate under the low temperature condition of 10 ℃ and constant current.
Example 4
In this comparative example, the difference from example 1 is the manner of formation of the battery:
the formation condition of the battery is charging for 3h at 0.05C rate under the normal temperature condition, then standing in a 50 ℃ oven for 20h, and then charging to 4.9V at 0.05C rate under the low temperature condition of-10 ℃ and constant current.
Example 5
In this comparative example, the difference from example 2 is the fabrication of a composite aluminum current collector:
the first corrosion inhibition conducting layer of the composite aluminum current collector comprises fluorinated polyacrylic resin and conductive fluorinated polypyrrole, wherein the mass ratio of the fluorinated polyacrylic resin to the conductive fluorinated polypyrrole is 1:3.
Example 6
In this comparative example, the difference from example 3 is the fabrication of a composite aluminum current collector and positive electrode:
the second conducting layer in the composite aluminum current collector comprises polyvinylidene fluoride carrying adamantane molecular chains, polyvinylidene fluoride and a graphite material. The positive adhesive is polyvinylidene fluoride and polyvinylidene fluoride carrying cyclodextrin molecular chains.
Fig. 1 is a schematic diagram of a high-voltage lithium ion positive electrode according to embodiments 1 to 6 of the present invention, where 1-1 is an upper positive electrode slurry layer, 1-2 is a lower positive electrode slurry layer, 2-1 is an upper second conductive layer, 2-2 is a lower second conductive layer, 3 is a metal current collector, 4-1 is an upper first corrosion-inhibiting conductive layer, and 4-2 is a lower first corrosion-inhibiting conductive layer.
Comparative example 1
This comparative example differs from example 1 only in that: the corrosion inhibitor in the first corrosion inhibition conducting layer is polyacrylic resin.
Comparative example 2
This comparative example differs from example 1 only in that: the conductive polymer in the first corrosion-inhibiting conductive layer is polypyrrole.
Comparative example 3
This comparative example differs from example 1 only in that: and in the second conducting layer, polyvinylidene fluoride is adopted to replace polyvinylidene fluoride of an adamantane molecular chain.
Comparative example 4
This comparative example differs from example 1 only in that: in the positive electrode slurry, polyvinylidene fluoride is adopted to replace polyvinylidene fluoride carrying cyclodextrin molecular chains.
Comparative example 5
This comparative example differs from example 1 only in that: the formation mode of the battery is different, and the formation mode of the battery of the comparative example is that the battery is charged to 4.9V at a rate of 0.05C and then discharged to 3V at a rate of 0.05C. Cycling was performed 3 times in a charge-discharge pattern.
Charge and discharge cycle test
Table 1 shows the results of charge and discharge cycle tests at normal temperature of 25℃ and at high temperature of 55℃ at 0.2C and 1C for the batteries prepared in examples 1 to 6 and comparative examples 1 to 4, respectively.
TABLE 1 Polymer lithium ion Battery Charge-discharge cycling test
Figure BDA0003090346240000101
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.

Claims (9)

1. An application of a high-voltage lithium ion positive electrode plate in the preparation of batteries is characterized in that,
the pole piece comprises a composite current collector and positive electrode slurry coated on the surface of the current collector; the composite current collector comprises a composite aluminum current collector; the composite aluminum current collector comprises an aluminum substrate with concave holes on the surface, and a first corrosion inhibition conducting layer and a second conducting layer which are respectively coated on two sides of the aluminum substrate; the first corrosion inhibition conducting layer is formed by blending a corrosion inhibitor and a conducting polymer; the HOMO value of the conductive polymer is less than-11 eV; the second conducting layer comprises a polymer binder I for carrying guest molecules, a polymer binder and conductive carbon which are blended; the HOMO value of the polymer binder I carrying the guest molecules is less than-11 eV;
the preparation method of the battery comprises the following steps:
s1: manufacturing a composite aluminum current collector: dissolving a corrosion inhibitor and a conductive polymer by using a solvent at 50-120 ℃ in an inert atmosphere to form a corrosion inhibition conductive solution; immersing an aluminum substrate with concave holes on the surface into a corrosion inhibition conducting solution, standing for 3-10 h, and evaporating the corrosion inhibition conducting solution to dryness at 60-150 ℃ to obtain an aluminum current collector coated with a first corrosion inhibition conducting layer; mixing a polymer binder I carrying guest molecules, a polymer binder, a conductive carbon material and a solvent to form a conductive slurry, and adjusting the viscosity of the slurry to be 1000-6000 mPa.S according to the using amount of the solvent; coating or screen printing the slurry on the surface of the first corrosion inhibition conductive layer of the aluminum current collector, and drying, wherein the guest molecule is adamantane;
s2: manufacturing a positive electrode: dissolving a polymer binder and a polymer binder II carrying main body molecules in NMP under a low dew point environment, so that the total concentration of the polymer binder and the polymer binder II carrying main body molecules is 1-8%; adding a positive electrode conductive agent, stirring at a high speed, adding a positive electrode active material, and continuously stirring at a high speed to form positive electrode slurry; coating the electrode slurry on a positive current collector, and after drying a solvent, rolling and punching the formed electrode to prepare a positive electrode; the host molecule is cyclodextrin;
s3: preparing a prelithiation negative electrode: dissolving a negative electrode binder in NMP (N-methyl pyrrolidone) in a low dew point environment to enable the concentration of the negative electrode binder to be 1-10%; adding a conductive agent and stirring at a high speed; adding a negative electrode active material, and continuously stirring to form negative electrode slurry; coating the electrode slurry on a negative current collector, drying a solvent, and rolling and punching the formed electrode to prepare a negative electrode; soaking the lithium foil with organic electrolyte, rolling the lithium foil onto the surface of a negative electrode, and standing;
s4: manufacturing a high-voltage lithium ion battery: under the low dew point environment, the prepared positive electrode, prelithiation negative electrode and diaphragm are laminated or coiled to prepare a dry cell, the tabs are welded and then packaged by an aluminum plastic film, and organic electrolyte is injected into the dry cell and then is pre-vacuumized to prepare a high-voltage lithium ion battery;
s5: formation of a battery: fixing the prepared high-voltage lithium ion battery tab, charging for 2-4h at the rate of 0.02C-0.5C under the condition of normal temperature, standing for 10-24h in an oven at the temperature of 40-55 ℃, and then charging for constant current at the rate of 0.02C-0.5C under the condition of low temperature of-10 ℃ to the cut-off potential; and (4) secondary vacuum-pumping of the battery.
2. The use of the high voltage lithium ion positive electrode sheet of claim 1 in the preparation of a battery, wherein the positive electrode slurry comprises an oxidation potential greater than 4.5V vs + The positive electrode active material, the positive electrode conductive agent, the polymer binder and the polymer binder II carrying the host molecule; the HOMO value of the polymer binder II carrying the host molecules is less than-11 eV; the positive electricity active material is one or more of lithium nickel manganese oxide, lithium iron manganese oxide, lithium cobalt phosphate and lithium nickel phosphate with olivine structures and lithium nickel vanadate with inverse spinel structures.
3. The application of the high-voltage lithium ion positive electrode plate in the preparation of the battery according to claim 1, wherein the corrosion inhibitor is one or more selected from fluorinated ethylene-vinyl acetate resin, fluorinated polyacrylic resin, fluorinated polystyrene resin, fluorinated acrylates and fluorinated phosphates; the conductive polymer is one or more of conductive fluorinated polypyrrole and conductive fluorinated polyurethane.
4. The use of the high-voltage lithium-ion positive electrode plate according to claim 2 in the preparation of a battery, wherein the polymer binder is selected from one or more of polyvinylidene fluoride, fluorinated epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene; the guest molecules in the guest molecule carrying polymer binder I are adamantane, and the polymer binder I is selected from one or more of polyvinylidene fluoride, fluorinated epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene; the main molecules of the polymer binder II carrying the main molecules are cyclodextrin, and the polymer binder II is selected from one or more of polyvinylidene fluoride, fluorinated epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene.
5. The application of the high-voltage lithium ion positive electrode plate in the preparation of the battery according to claim 1, wherein the thickness of the first corrosion inhibition conducting layer is 10nm to 100nm; the mass ratio of the corrosion inhibitor to the conductive polymer is 1 to 1; the thickness of the second conducting layer is 0.1-10 μm; the mass ratio of the polymer binder I carrying the guest molecules to the polymer binder and the conductive carbon is 1.
6. The application of the high-voltage lithium-ion positive electrode plate in the preparation of the battery according to claim 1, wherein in the step S1, the mass ratio of the sum of the mass of the corrosion inhibitor and the mass of the conductive polymer to the mass of the solvent is 1; the solvent is selected from one of tetrahydrofuran, amyl acetate and dimethyl sulfoxide strong-polarity organic solvents; the volume ratio of the corrosion inhibition conducting solution to the aluminum base material is (2).
7. The application of the high-voltage lithium ion positive electrode plate in the preparation of the battery according to claim 1, wherein in the step S2, the positive electrode active material accounts for 80-96% by mass of the positive electrode slurry, the positive electrode conductive agent accounts for 2-10% by mass of the positive electrode slurry, the polymer binder II carrying the host molecule accounts for 1~5% by mass of the polymer binder, and the polymer binder accounts for 1~5% by mass of the polymer binder; the positive electrode conductive agent is a combined conductive agent and comprises a granular conductive agent, a linear conductive agent and a sheet conductive agent, wherein the granular conductive agent is one or more of super carbon black, conductive carbon black, ks-6 and Ks-15, the linear conductive agent is one or more of VGCF and carbon nano tubes, and the sheet conductive agent is graphene.
8. The application of the high-voltage lithium-ion positive electrode plate in the preparation of the battery according to claim 1, wherein in the step S3, the negative electrode active material is a graphite material, and the proportion of the negative electrode active material is 90-98% by mass of the negative electrode slurry; the negative electrode conductive agent is selected from one or more of super carbon black, conductive carbon black, ks-6 and Ks-15, and the proportion of the negative electrode conductive agent is 1-5%; the negative electrode binder is selected from polyvinylidene fluoride and fluorineOne or more of epoxy resin, fluorinated phenolic resin, fluorinated polyvinyl alcohol and polytetrafluoroethylene are added, and the proportion of the negative electrode binder is 1% -5%; the organic electrolyte is a perfluorinated organic electrolyte, wherein the solvent is selected from any three or more of FEC, FEMC, HFE, FDMC and TFEC, but at least comprises HFE and FEMC, the solute is a mixed lithium salt, and the solute comprises any two or more of lithium hexafluorophosphate, liODFB and LiBOB, but at least comprises LiODFB; the oxidation potential of the organic electrolyte is more than 5V, and the conductivity is more than 5.5S/cm 2 。
9. The application of the high-voltage lithium-ion positive electrode plate in the preparation of the battery according to claim 1, wherein the membrane in the step S4 is a coated membrane, the membrane substrate is PE or PP, and the coating is PVDF or metal oxide; the thickness of the diaphragm is 5nm to 200nm; the organic electrolyte comprises 50-70% of FEMC in terms of volume percentage, 10-40% of HFE in terms of volume percentage and 1-10% of LiODFB in terms of molar ratio in terms of solute.
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