CN113097448A - Lithium-supplementing negative electrode and application thereof - Google Patents

Lithium-supplementing negative electrode and application thereof Download PDF

Info

Publication number
CN113097448A
CN113097448A CN202110354024.7A CN202110354024A CN113097448A CN 113097448 A CN113097448 A CN 113097448A CN 202110354024 A CN202110354024 A CN 202110354024A CN 113097448 A CN113097448 A CN 113097448A
Authority
CN
China
Prior art keywords
lithium
negative electrode
supplement
layer
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110354024.7A
Other languages
Chinese (zh)
Inventor
邱昭政
李文龙
赵育松
赵俊年
梁世硕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunshan Bao Innovative Energy Technology Co Ltd
Original Assignee
Kunshan Bao Innovative Energy Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kunshan Bao Innovative Energy Technology Co Ltd filed Critical Kunshan Bao Innovative Energy Technology Co Ltd
Priority to CN202110354024.7A priority Critical patent/CN113097448A/en
Publication of CN113097448A publication Critical patent/CN113097448A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a lithium-supplementing negative electrode and application thereof, wherein the lithium-supplementing negative electrode comprises a negative electrode current collector, a negative electrode active layer arranged on at least one functional surface of the negative electrode current collector and a lithium-supplementing layer arranged on the surface of the negative electrode active layer; the lithium supplement layer comprises lithium powder and a lithium ion conductive agent. The lithium supplement negative electrode can not only efficiently supplement the active lithium loss of the lithium ion battery, but also greatly reduce the risk of lithium precipitation caused by lithium supplement, and ensure the cycle performance and safety of the lithium ion battery in the long-term application process.

Description

Lithium-supplementing negative electrode and application thereof
Technical Field
The invention relates to a negative plate, in particular to a lithium-supplementing negative electrode and application thereof, and belongs to the technical field of secondary batteries.
Background
A lithium ion battery is a secondary battery that is very widely used. At present, the lithium ion battery mainly comprises an anode, a cathode, a diaphragm and electrolyte. In a specific application process, lithium ions are consumed due to the generation of an SEI film, the falling-off of a negative electrode active material, and the like. In addition, as the demand for energy density of lithium ion batteries is higher, silicon-oxygen-based materials are gradually used as negative electrode active materials with higher capacity in lithium ion batteries, but the silicon-oxygen-based materials form lithium oxides during the process of lithium intercalation for the first time, which results in large lithium consumption. Further, the first charge-discharge efficiency of the lithium ion battery is difficult to meet the requirements due to lithium consumption, and the improvement of the capacity exertion of the lithium ion battery is influenced.
At present, a lithium supplement method is mostly adopted to solve the problems, the first charge-discharge efficiency of the lithium ion battery is improved, and the cycle performance of the lithium ion battery is improved. Lithium is more commonly supplemented to the negative electrode in the reported lithium supplementing means at present.
The negative electrode lithium supplement refers to that lithium powder and a negative electrode active material are mixed to serve as a negative electrode active layer, or a lithium supplement layer containing the lithium powder is arranged on a negative electrode plate, however, the lithium precipitation risk can be caused by the increase of the content of the lithium powder, so that the lithium supplement efficiency of a negative electrode lithium supplement method is not high, and the improvement range of the first charge-discharge efficiency and the cycle performance of the lithium ion battery is limited.
Disclosure of Invention
The invention provides a lithium supplement negative electrode which can not only effectively supplement active lithium loss of a lithium ion battery, but also greatly reduce the risk of lithium precipitation caused by lithium supplement, and ensure the cycle performance and safety of the lithium ion battery in the long-term application process.
The invention also provides a lithium ion battery, which contains the lithium-supplementing cathode, so that the lithium ion battery has both excellent cycle performance and safety performance.
The invention provides a lithium-supplementing negative electrode which comprises a negative electrode current collector, a negative electrode active layer arranged on the surface of the negative electrode current collector and a lithium-supplementing layer arranged on the surface of the negative electrode active layer;
the lithium supplement layer comprises lithium powder and a lithium ion conductive agent.
In the lithium supplement negative electrode, the lithium supplement layer is used for releasing active lithium into the lithium ion battery so as to supplement lithium loss in the application process of the lithium ion battery, so that the first effect of the lithium ion battery is improved, and excellent cycle performance is shown. In addition, the lithium ion conductive agent in the lithium supplement layer can improve the lithium ion diffusion capacity of the lithium supplement negative electrode, the lithium precipitation phenomenon caused by the aggregation of lithium ions in the lithium ion battery on the surface of the lithium supplement negative electrode is avoided, the cycle performance of the lithium ion battery is further improved by inhibiting the growth of lithium dendrites, and a safer environment is provided for the application of the lithium ion battery.
The lithium-doped negative electrode as described above, wherein the lithium ion conductive agent is selected from the group consisting of lithium lanthanum titanium oxide compound, lithium lanthanum zirconium oxide compound, sulfide solid electrolyte and Li1+xAlxM2－x(PO4)3M is selected from at least one of Ti, Ga, Sc, In, Y and Ge, and x is more than or equal to 0.01 and less than or equal to 1.0.
The lithium supplement negative electrode is characterized in that the lithium supplement layer comprises 15-80% of lithium powder by mass and 20-85% of lithium ion conductive agent by mass. The lithium supplementing layer can supplement lithium to the lithium ion battery efficiently in a safe environment, and the phenomenon that lithium dendrites are separated out due to excessive lithium powder is avoided.
The lithium-supplement negative electrode as described above, wherein the lithium-supplement layer is formed of a lithium-supplement materialThe loading capacity of the lithium powder is 0.05-1.0mg/cm2. The loading capacity is beneficial to maintaining the uniform distribution of lithium ions in the lithium ion battery, and the probability of lithium dendrite precipitation is further reduced.
The lithium-supplement negative electrode has the advantages that the particle size of the lithium ion conductive agent is 100-2000 nm. The particle size is beneficial to the uniform distribution of the lithium ion conductive agent in the lithium supplement layer, and further improves the lithium ion diffusion capacity.
The lithium-compensated negative electrode as described above, wherein the lithium-compensated layer further comprises inorganic particles. Inorganic particles in the lithium supplement layer can prevent the lithium powder in the lithium supplement layer from agglomerating, so that the lithium powder can be more uniformly distributed in the lithium supplement layer, and the risk of lithium precipitation is reduced.
The lithium-doped negative electrode as described above, wherein the lithium-doped layer further comprises an electron conductive agent. The electronic conductive agent can establish a conductive network in the lithium supplement layer and between the lithium supplement layer and the negative active layer, and smooth transmission of electrons is guaranteed.
The lithium-compensated negative electrode as described above, wherein the lithium-compensated layer further comprises a binder. The binder is used for maintaining the structural stability of the lithium supplement layer and avoiding negative influence on the cycle performance of the lithium ion battery caused by the falling of the lithium supplement layer.
The lithium supplement negative electrode comprises the following lithium supplement layers in percentage by mass: 15-70 wt% of lithium powder, 15-55 wt% of lithium ion conductive agent, 10-30 wt% of inorganic particles, 0.5-4.0 wt% of electronic conductive agent and 1.0-5.0 wt% of binder. The composition is beneficial to further improving the cycle performance of the lithium ion battery.
The invention also provides a lithium ion battery which comprises the lithium supplement negative electrode. The lithium ion battery can show more excellent cycle performance and safety performance.
The lithium supplement negative electrode comprises the lithium supplement layer arranged on the surface of the negative electrode active layer, the lithium supplement layer can release active lithium to improve the cycle performance of the lithium ion battery, the lithium ion conductive agent in the lithium supplement layer can improve the lithium ion diffusion capacity in the lithium supplement negative electrode, and the lithium dendrite phenomenon caused by excessive deposition of lithium ions on the lithium supplement negative electrode interface is inhibited to a certain extent, so that the influence of the lithium dendrite on the cycle performance of the lithium ion battery is avoided, the probability of battery short circuit caused by contact of a positive electrode and a negative electrode is reduced, and the safety performance of the lithium ion battery is ensured.
Drawings
Fig. 1 is a schematic structural diagram of a lithium-supplement negative electrode according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a schematic structural diagram of a lithium-supplement negative electrode according to an embodiment of the present invention. As shown in fig. 1, the lithium supplement negative electrode of the present invention includes a negative electrode current collector 1, a negative electrode active layer 2 disposed on at least one surface of the negative electrode current collector 1, and a lithium supplement layer 3 disposed on a surface of the negative electrode active layer;
the lithium supplement layer 3 includes lithium powder and a lithium ion conductive agent.
The functional surfaces of the negative current collector 1 refer to two largest and oppositely arranged surfaces for arranging the negative active layer 2 in the negative current collector 1, and in the lithium supplement negative electrode of the present invention, the negative active layer 2 may be arranged on only one functional surface of the negative current collector 1, or may be arranged on two functional surfaces of the negative current collector 1 at the same time. In fig. 1, the negative electrode active layer 2 is provided on only one functional surface of the negative electrode current collector 1.
In the lithium-replenishing negative electrode of the present invention, the lithium replenishing layer 3 for replenishing lithium is provided on the surface of the negative electrode active layer 2 remote from the negative electrode fluid 1. The lithium supplement layer 3 comprises lithium powder and a lithium ion conductive agent, wherein the lithium powder is used for providing lithium ions for the lithium ion battery so as to supplement the loss of active lithium in the system caused by the first charge and discharge, SEI film formation or other irreversible reactions of the lithium ion battery; the lithium ion conductive agent is used for improving the diffusion capacity of lithium ions in the lithium supplement negative electrode, so that more lithium ions can enter the lithium supplement layer 3 or the negative electrode active layer 2 and are embedded, the potential safety hazard caused by the fact that interface lithium dendrites grow to pierce a diaphragm or solid electrolyte is avoided, and the negative influence of lithium dendrites and even 'dead lithium' on the cycle performance of the lithium ion battery is remarkably reduced. In addition, by increasing the migration rate of lithium ions in the lithium-supplement negative electrode, the lithium ion conductive agent also plays a role in reducing the polarization phenomenon of the lithium-supplement negative electrode, so that the charge-discharge efficiency of the lithium-supplement negative electrode and the service life of the lithium ion battery are improved to a certain extent.
Therefore, the lithium supplement negative electrode can complete lithium supplement operation on the lithium ion battery under extremely low risk of lithium precipitation, and reduces the safety risk caused by lithium supplement, thereby prolonging the service life of lithium ions.
The present invention is not limited to a specific kind of the lithium ion conductive agent, and may be selected from, for example, lanthanum titanium oxide compound, lithium lanthanum zirconium oxide compound, sulfide solid electrolyte and Li1+xAlxM2－x(PO4)3M is selected from at least one of Ti, Ga, Sc, In, Y and Ge, and x is more than or equal to 0.01 and less than or equal to 1.0. Illustratively, the sulfide solid electrolyte may be Li10GeP2S12、Li10SnP2S12、Li3.25Ge0.25P0.75S4And the like. Further, Li1+xAlxM2－x(PO4)3May be of the NASICON type.
The lithium powder in the lithium supplement layer 3 can be metal lithium powder or inert lithium powder. The inert lithium powder is a material with a core-shell structure and comprises a metal lithium or lithium alloy inner core and an inert layer at least covering the surface of the inner core. The lithium alloy means an alloy of lithium with other metals, for example, an alloy lithium alloy with Mg, Al, Zn, K, Cu, Na, or the like; the inert layer is selected from organic polymer, organic small molecule compound and Li2CO3、LiF、Li2At least one of S, LiCl and Li-Si alloy. In the concrete implementation processInert lithium powder may be selected because the inert layer of inert lithium powder is capable of coupling the highly reactive lithium powder to the external environment, e.g., H2O and O2And the isolation is carried out, so that the risks of fire, combustion and the like caused by the use of the lithium powder are reduced.
Optionally, the particle size of the lithium powder in the lithium supplement layer is 2-50 μm.
In the lithium-supplement negative electrode, the mass percentage of the lithium powder in the lithium-supplement layer 3 is 15-80%, and the mass percentage of the lithium ion conductive agent in the lithium-supplement layer 3 is 20-85%. As described above, the existence of the lithium ion conductive agent can reduce the safety risk brought by lithium supplement to the lithium ion battery to a certain extent, so the lithium supplement layer 3 formed in the above manner can supplement lithium to the lithium ion battery to different extents on the premise that the safety is ensured, and of course, the specific content of the lithium powder can be further determined according to the specific application environment and the application requirement of the lithium ion battery. For example, the lithium supplement layer of the present invention may contain high content of 60% of lithium powder, that is, on the basis of not sacrificing safety performance, the lithium supplement effect is further optimized by increasing the content of the lithium powder to a certain extent, and lithium loss is supplemented to a large extent to prolong the cycle life of the lithium ion battery.
In one embodiment, lithium powder and a lithium ion conductive agent may be mixed in an organic solvent according to the above composition to prepare a lithium supplement slurry, and then the lithium supplement slurry is coated on the surface of the negative electrode active layer 2 away from the negative electrode current collector 1, and after drying and rolling, the lithium supplement negative electrode having the above lithium supplement layer 3 is obtained.
Furthermore, the loading capacity of the lithium powder is 0.05-1.0mg/cm2. The lithium powder loading in the invention refers to the mass of lithium powder in each square centimeter of lithium supplement layer. It can be understood that on the premise that the lithium can be safely supplemented, the more the lithium powder loading amount per unit area is, the better the lithium supplementing effect is, so that on the premise that the lithium powder quality in the lithium supplementing layer 3 is certain, the loading amount of the lithium powder can be realized by controlling the thickness of the lithium supplementing layer 3 and the like, and the cycle performance of the lithium ion battery can be further improved.
Optionally, the particle size of the 3 lithium ion conductive agent in the lithium supplement layer is 100-2000 nm. The inventor researches and discovers that the lithium ion conductive agent with the particle size is beneficial to uniformly dispersing the lithium ion conductive agent in the lithium supplement layer 3, so that lithium ions are more uniformly inserted into the negative electrode active layer 2 through further improvement of lithium ion diffusion capacity, and lithium separation caused by contention of lithium ions for insertion sites of a negative electrode interface is more favorably avoided.
The lithium supplement layer 3 in the lithium supplement negative electrode of the invention can comprise other auxiliary agents besides the lithium powder and the lithium ion conductive agent so as to further improve the performance of the lithium supplement negative electrode and optimize the lithium supplement effect of the lithium supplement negative electrode.
In one embodiment, the lithium supplement layer 3 further includes inorganic particles, illustratively lithium titanate, Cu oxide, Al oxide, zirconium oxide, Co oxide, Fe oxide, zinc oxide, Ni oxide, V oxide, Sn oxide, Mn oxide, Mo oxide, Si oxide, LiF, Li oxide, boehmite, CaCO, and inorganic particles3、Li2CO3、MgCO3One or more of them. Particularly, in the process of preparing the lithium supplementing layer 3, the inorganic particles are added into the lithium supplementing slurry, so that the uniform dispersion of the lithium powder can be ensured, the influence of the lithium powder on the flatness of the surface of the lithium supplementing layer 3 is avoided, the consistency of the lithium supplementing degree inside the lithium ion battery is ensured, the probability of separation of lithium dendrites is further reduced, and the cycle performance and the safety performance of the lithium ion battery are ensured.
Further, the particle size of the inorganic particles is 0.1 to 5 μm, which is more advantageous for the performance of the inorganic particles. Too small or too large a particle size may affect its dispersing effect on the lithium powder to some extent.
In one embodiment, the lithium supplement layer 3 further includes an electron conductive agent. The addition of the electron conductive agent can connect the components in the lithium supplement layer 3 together, so that the components can still be electrically contacted to form a conductive path, thereby forming a conductive network in the lithium supplement layer 3. The conductive network can rapidly lead out electrons in the lithium-supplement negative electrode to realize the charge and discharge of the lithium ion battery under high current, reduce the polarization phenomenon of the lithium-supplement negative electrode in the high-rate charge and discharge process, inhibit the increase of the internal resistance of the lithium ion battery in the long-term circulation process, and be beneficial to improving the performance of the lithium ion battery in the aspect of power batteries. In addition, the rapid derivation of electrons by the conductive network can also reduce the probability that lithium ions are combined with electrons to be reduced, and further reduce the possibility of lithium analysis.
The present invention is not limited to the specific selection of the electron conductive agent, and may be selected from inorganic electron conductive agents and/or organic electron conductive agents. The inorganic electronic conductive agent is selected from at least one of conductive carbon black, conductive graphite, Acetylene Black (AB), carbon fiber (VCF), Vapor Grown Carbon Fiber (VGCF), Carbon Nano Tube (CNTs), Ketjen black, graphene, Mxene, porous carbon, copper powder, silver powder, nickel powder, tin oxide, iron oxide, zinc oxide and the like, and the organic electronic conductive agent is selected from at least one of polyaniline, polythiophene, polypyrrole, polyacetylene, polyphenylene, polyphenyl and conductive polymer compound.
In one embodiment, the lithium supplement layer 3 further includes a binder. In the process of long-term circulation of lithium ions, once the lithium-supplement negative electrode falls off, for example, a part of the lithium-supplement layer 3 falls off, the newly exposed lithium-supplement negative electrode interface reacts with the electrolyte, which not only causes consumption of the electrolyte and the lithium ions, but also causes expansion of the lithium ion battery due to factors such as gas generation and the like, thereby affecting the safety performance. Therefore, the invention adds the binder into the lithium supplement layer 3 to bind other components in the lithium supplement layer 3, such as lithium powder, lithium ion conductive agent, inorganic particles and electrode conductive agent together, thereby avoiding the falling-off of part of the lithium supplement layer 3 in the long-term application process of the lithium supplement negative electrode, and being beneficial to avoiding the falling-off of the lithium supplement layer 3 equivalent to the negative electrode active layer.
In addition, the binder is also beneficial to ensuring the uniform dispersion of the lithium powder in the lithium supplement layer 3. In the process of preparing the lithium supplement layer 3, because the density of the lithium powder is too low to keep stable dispersion in the lithium supplement slurry, and the addition of the binder can increase the viscosity of the lithium supplement slurry, so that the lithium powder is uniformly suspended in the lithium supplement slurry and is kept stable for a long time, thereby being beneficial to obtaining the lithium supplement layer 3 with uniformly distributed lithium powder, and further reducing the probability of lithium dendrite precipitation by realizing the consistency of the lithium supplement degree in the lithium ion battery.
The present invention is not limited to the specific selection of the binder, and examples thereof include at least one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene-butadiene rubber (SBR), Polystyrene (PS), Nitrile Butadiene Rubber (NBR), polyethylene, and polypropylene.
It can be understood that when different lithium powders, lithium ion conductive agents, inorganic particles, electron conductive agents and binders are used in the lithium supplement layer 3, even different cathode active materials, anode active materials and electrolytes are used, the final performance of the lithium ion battery is affected. Therefore, in general, in the case of the above-mentioned different lithium powder, lithium ion conductive agent, inorganic particles, electron conductive agent, binder, positive electrode active material, negative electrode active material, and electrolyte, when the lithium supplement layer 3 includes, by mass, 15 to 70 wt% of lithium powder, 15 to 55 wt% of lithium ion conductive agent, 10 to 30 wt% of inorganic particles, 0.5 to 4.0 wt% of electron conductive agent, and 1.0 to 5.0 wt% of binder, the lithium supplement performance and safety performance can be substantially optimized.
Particularly, when the lithium supplement layer of the lithium powder, the lithium ion conductive agent, the inorganic particles, the electron conductive agent and the binder is prepared, the components are more, so that the components are required to be rapidly and stably dispersed in the solvent to form lithium supplement slurry. In one embodiment, the binder may be added to the wastewater solvent to form a glue solution, and then the electronic conductive agent, the inorganic particles and the lithium powder are sequentially added to the glue solution to obtain the lithium-supplemented slurry. In another embodiment, the non-aqueous solvent is divided into three parts, the conductive agent, the inorganic particles and the binder are respectively added into the three parts of the non-aqueous solvent for homogenization, then the three parts of the slurry are mixed and homogenized, and finally the lithium powder is added to obtain the lithium supplement slurry. In another embodiment, the conductive agent and the inorganic particles are mixed uniformly and then added into partial non-aqueous solvent, and the mixture is homogenized to obtain slurry; adding the binder into the residual non-aqueous solvent, and homogenizing to obtain slurry; and mixing the two parts of slurry, adding lithium powder, and homogenizing to obtain the lithium supplementing slurry. Wherein the non-aqueous solvent is at least one selected from propylene carbonate, dimethyl carbonate, diethyl carbonate, acetone, DMSO, chloroform, acetonitrile, tetrahydrofuran, ethyl methyl carbonate, toluene, xylene, N-dimethylformamide and N-methylpyrrolidone; homogenizing includes, but is not limited to, magnetic stirring, ultrasonic homogenizing, ball milling, top or bottom mounted paddle shear stirring, and the like.
And after lithium supplement slurry is obtained, coating the lithium supplement slurry on the surface of the negative active layer 2 far away from the negative current collector 1, and drying and rolling to obtain the lithium supplement negative electrode. On the one hand, the roll-in operation can be pressed into the lithium sheetmetal of flat shape with spherical lithium powder this area that can increase lithium powder and negative pole active material layer, and on the other hand the distance between lithium powder and the negative pole active material layer shortens after the roll-in and is favorable to mending the acceleration of lithium process, and on the other hand the packing density of mending lithium layer 3 after the roll-in increases the electric conduction network more closely on the one hand and can further improve the conductivity of mending lithium layer 3, improves interfacial impedance, promotes the interfacial properties of mending the lithium negative pole.
In order to facilitate coating of the lithium supplement slurry on the surface of the negative electrode active layer 2 and ensure flatness of an interface of the lithium supplement layer 3 formed by drying the lithium supplement slurry, the using amount of the non-aqueous solvent can be controlled so that the solid content of the lithium supplement slurry is 15-55 wt%, and the viscosity is 1000-3700 mPa ≤. On the basis of ensuring the fluidity of the lithium supplementing slurry and the flatness of a coated lithium supplementing layer, the solid content is properly improved, the using amount of a wastewater solvent can be reduced, the generation of waste liquid is reduced, and the speed of the coating process can be increased, so that the energy consumption is reduced.
In addition, the present invention is not limited to the method for preparing the negative electrode active layer 2, and for example, the negative electrode active material, the binder, and the conductive agent are added to the non-aqueous solvent and homogenized to obtain a negative electrode active slurry, and the negative electrode active slurry is coated on at least one functional surface of the negative electrode current collector 1 and then dried to obtain the negative electrode active layer 2 disposed on the functional surface 1 of the negative electrode current collector.
The present invention is not limited to the above-described negative electrode active material, and may be a negative electrode active material commonly used in lithium ion batteries at present, such as at least one of graphite, a soft carbon material, a hard carbon material, an amorphous carbon material, a silicon oxygen material, a transition metal oxide, and the like.
The binder in the negative electrode active slurry is at least one selected from the group consisting of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene-butadiene rubber (SBR), Polystyrene (PS), Nitrile Butadiene Rubber (NBR), polyethylene, and polypropylene, the conductive agent is at least one selected from conductive carbon black, conductive graphite, Acetylene Black (AB), carbon fiber (VCF), Vapor Grown Carbon Fiber (VGCF), Carbon Nanotubes (CNTs), Ketjen black, graphene, Mxene, porous carbon, copper powder, silver powder, nickel powder, tin oxide, iron oxide, zinc oxide, and the like, and the non-aqueous solvent may be at least one selected from propylene carbonate, dimethyl carbonate, diethyl carbonate, acetone, DMSO, chloroform, acetonitrile, tetrahydrofuran, ethyl methyl carbonate, toluene, xylene, N-dimethylformamide, and N-methylpyrrolidone.
The invention also provides a lithium ion battery which comprises the lithium supplement negative electrode.
Of course, the lithium-ion-doped negative electrode also comprises a positive electrode, an electrolyte and a separator.
The invention does not strictly limit the positive active material in the positive electrode, and can be at least one of the positive active materials commonly used in the current lithium ion battery, such as lithium iron phosphate (LFP), lithium cobaltate, lithium nickelate, nickel-cobalt binary material, nickel-cobalt-manganese ternary material, nickel-cobalt-aluminum ternary material, and the like.
The present invention does not strictly limit the specific composition of the electrolytic solution, and includes, for example, at least an organic solvent and a lithium salt. For example, the organic solvent is selected from at least one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, Ethyl Methyl Carbonate (EMC), Vinylene Carbonate (VC), Propylene Carbonate (PC), butylene carbonate, fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), dimethyl fluorocarbonate, ethyl methyl fluorocarbonate, Vinyl Ethylene Carbonate (VEC), propyl butyrate, fluoroether HFPM, fluoroether MFE, fluoroether EME, Acetonitrile (AN), Glutaronitrile (GN), Adiponitrile (ADN), malononitrile, Tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1, 3-Dioxolan (DOL), 1, 4-Dioxane (DOX), sulfolane, dimethyl sulfoxide (DMSO), and the like, the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium tris (difluoromalonate) phosphate (litfmp), lithium tetrafluoro oxalate phosphate (litfip), lithium hexafluoroarsenate (LiAsF)6) Lithium hexafluoroantimonate (LiSbF)6) Lithium difluorophosphate (LiPF)2O2) At least one of lithium bis (oxalato) borate (LiBOB), lithium (malonato oxalato) borate (LiMOB), lithium (difluoromalonato oxalato) borate (LiDFMOB), lithium (malonato) borate (LiBMB), lithium (difluorooxalato) borate (liddfob), lithium (difluoromalonato) borate (libfmb), lithium tris (oxalato) phosphate (LiTOP), and the like.
The lithium ion battery of the invention can show excellent cycle performance and safety performance because of comprising the lithium-supplement negative electrode.
Hereinafter, the lithium-complementary negative electrode and the lithium ion battery according to the present invention will be described in detail by way of specific examples.
Example 1
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1%, lithium ion conductive agent Li with the particle size of D50 ═ 500nm7La3Zr2O12Electron conductive agents SP and Al2O3Dissolving the binder PTFE and the inert lithium powder in the NMP solution to form a lithium supplementation slurry with the solid content of 38.2 wt% and the viscosity of 2400mPa ≤;
the solid (non-NMP solution) in the lithium supplement slurry comprises the following components in percentage by mass: 35 wt% of lithium ion conductive agent LLZO, 2.0 wt% of conductive agent SP, Al2O320 wt%, binder PTFE 3% and inert lithium powder 40%.
2. Negative electrode active paste
Mixing a silicon-oxygen negative electrode and graphite to prepare a negative electrode material (named as SiO-500) with the specific capacity of 500mAh/g, mixing the SiO-500, a conductive agent SP and a binder according to the mass ratio of 92:4:4, and adding a proper amount of NMP to obtain negative electrode active slurry;
3. lithium-supplementing negative electrode
Coating the cathode active slurry on the upper surface of a Cu foil, drying and rolling to form a cathode active layer, wherein the surface density of the cathode active layer is 6.0mg/cm2The compacted density is 1.5g/cm3；
And coating the lithium supplement slurry on the surface of the negative electrode active layer by adopting a transfer coating method, drying and rolling to obtain the lithium supplement negative electrode.
The lithium powder loading capacity is 0.3mg/cm2。
The method for calculating the lithium powder loading capacity comprises the following steps: and (3) weighing the mass of the pole piece before and after the step (3), calculating the mass of the lithium supplement layer in unit area, and obtaining the loading capacity of the lithium powder in unit area according to the mass percentage content of the lithium powder in the lithium supplement layer.
Example 2
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1%, lithium ion conductive agent Li with the particle size of D50-700 nm1.5Al0.5Ge1.5(PO4)3(LATP), electron conductive agent CNT, SiO2Dissolving PVDF serving as a binder and inert lithium powder in an NMP solution to form a lithium supplementation slurry with solid content of 45.2 wt% and viscosity of 2400mPa ≤;
the lithium supplement slurry comprises the following solids in percentage by mass: lithium ion conductive agent LATP 40%, conductive agent CNT 0.5%, SiO221.5 percent, 3 percent of binder PVDF and 35 percent of inert lithium powder.
2. Negative electrode active paste
Same as example 1;
3. lithium-supplementing negative electrode
Coating the cathode active slurry on the upper surface of a Cu foil, drying and rolling to form a cathode active layer, wherein the surface density of the cathode active layer is 8.0mg/cm2Compacted density of 1.4g/cm3；
And coating the lithium supplement slurry on the surface of the negative electrode active layer by adopting a transfer coating method, drying and rolling to obtain the lithium supplement negative electrode.
The lithium powder loading capacity is 0.4mg/cm2。
Example 3
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1%, lithium ion conductive agent Li with the particle size of D50 ═ 400nm1.5Al0.5Ge1.5(PO4)3(lag), electron conducting agent SP, boehmite, binder PTFE, and inert lithium powder were dissolved in NMP solution to form a lithium supplemented slurry with a solids content of 32 wt% and a viscosity of 1900mPa ≤;
the lithium supplement slurry comprises the following solids in percentage by mass: 25 wt% of lithium ion conductive agent LAGP, 0.5 wt% of conductive agent SP, 22.5 wt% of boehmite, 2% of binder PTFE and 50 wt% of inert lithium powder.
2. Negative electrode active paste
Same as example 1;
3. lithium-supplementing negative electrode
Coating the cathode active slurry on the upper surface of a Cu foil, drying and rolling to form a cathode active layer, wherein the surface density of the cathode active layer is 12.0mg/cm2The compacted density is 1.5g/cm3；
And coating the lithium supplement slurry on the surface of the negative electrode active layer by adopting a transfer coating method, drying and rolling to obtain the lithium supplement negative electrode.
The lithium powder loading capacity is 0.8mg/cm2。
Example 4
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1%, the lithium ion conductive agent Li with the particle size of D50-800 nm7La3Zr2O12(LLZO), electron conductive agent SP, Al2O3Dissolving PVDF as binder and inert lithium powder in NMP solution to form a lithium supplementing slurry with solid content of 37.2 wt% and viscosity of 2100mPa ≤;
the lithium supplement slurry comprises the following solids in percentage by mass: lithium ion conductive agent LLZO 20%, electronic conductive agent SP 2.0 wt%, Al2O335 wt%, binder PVDF 4 wt% and inert lithium powder 39 wt%.
2. Negative electrode active paste
Same as example 1;
3. lithium-supplementing negative electrode
Coating the cathode active slurry on the upper surface of a Cu foil, drying and rolling to form a cathode active layer, wherein the surface density of the cathode active layer is 6.0mg/cm2The compacted density is 1.5g/cm3；
And coating the lithium supplement slurry on the surface of the negative electrode active layer by adopting a transfer coating method, drying and rolling to obtain the lithium supplement negative electrode.
The lithium powder loading capacity is 0.3mg/cm2。
Example 5
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
Same as in example 1
2. Negative electrode active paste
Mixing a silicon-oxygen negative electrode and graphite to prepare a negative electrode material (named as SiO-600) with specific capacity of 600mAh/g, mixing the SiO-600, a conductive agent SP and a binder according to a mass ratio of 92:4:4, and adding a proper amount of NMP to obtain negative electrode active slurry;
3. lithium-supplementing negative electrode
Coating the cathode active slurry on the upper surface of a Cu foil, drying and rolling to form a cathode active layer, wherein the surface density of the cathode active layer is 6.0mg/cm2The compacted density is 1.5g/cm3；
And coating the lithium supplement slurry on the surface of the negative electrode active layer by adopting a transfer coating method, drying and rolling to obtain the lithium supplement negative electrode.
The lithium powder loading capacity is 0.3mg/cm2。
Example 6
This example is essentially the same as example 1, except that the lithium-supplemented negative electrode of this example had a compacted density of 1.4g/cm3。
Example 7
This example is substantially the same as example 1, except that the lithium-supplementing layer thickness was controlled so that the lithium powder loading in the lithium-supplementing negative electrode was 0.5mg/cm2。
Example 8
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1%, lithium ion conductive agent Li with the particle size of D50-700 nm7La3Zr2O12Dissolving the binder PTFE and the inert lithium powder in NMP solution to form a lithium supplementing slurry with the solid content of 38.2 wt% and the viscosity of 3100mPa ≤;
the lithium supplement slurry comprises the following solids in percentage by mass: 55 wt% of lithium ion conductive agent LLZO, 4% of binder PTFE and 41% of inert lithium powder.
2. Negative electrode active paste
Same as example 1;
3. lithium-supplementing negative electrode
Same as in example 1.
The lithium powder loading capacity is 0.3mg/cm2。
The method for calculating the lithium powder loading capacity comprises the following steps: and (3) weighing the mass of the pole piece before and after the step (3), calculating the mass of the lithium supplement layer in unit area, and obtaining the loading capacity of the lithium powder in unit area according to the mass percentage content of the lithium powder in the lithium supplement layer.
Example 9
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1%, the lithium ion conductive agent Li with the particle size of D50-800 nm7La3Zr2O12(LLZO), electron conductive agent SP, binder PTFE, and inert lithium powder were dissolved in NMP solution to form a lithium supplemented slurry with a solids content of 37.5 wt% and a viscosity of 2900mPa ≤;
the lithium supplement slurry comprises the following solids in percentage by mass: 35 wt% of lithium ion conductive agent LLZO, 2.0% of conductive agent SP, 3% of adhesive PTFE and 60% of inert lithium powder.
2. Negative electrode active paste
Same as example 1;
3. lithium-supplementing negative electrode
The same as in the examples.
Lithium powder loadingThe amount is 0.3mg/cm2。
The method for calculating the lithium powder loading capacity comprises the following steps: and (3) weighing the mass of the pole piece before and after the step (3), calculating the mass of the lithium supplement layer in unit area, and obtaining the loading capacity of the lithium powder in unit area according to the mass percentage content of the lithium powder in the lithium supplement layer.
Example 10
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1%, the lithium ion conductive agent Li with the particle size of D50-800 nm7La3Zr2O12(LLZO)、Al2O3Binder PTFE and inert lithium powder were dissolved in NMP solution to form a lithium supplemented slurry with solids content of 40.7 wt% and viscosity of 2800mPa ≤;
the lithium supplement slurry comprises the following solids in percentage by mass: 35 wt% of lithium ion conductive agent LLZO and Al2O320 wt%, binder PTFE 3% and inert lithium powder 42%.
2. Negative electrode active paste
Same as example 1;
3. lithium-supplementing negative electrode
Same as in example 1.
The lithium powder loading capacity is 0.3mg/cm2。
The method for calculating the lithium powder loading capacity comprises the following steps: and (3) weighing the mass of the pole piece before and after the step (3), calculating the mass of the lithium supplement layer in unit area, and obtaining the loading capacity of the lithium powder in unit area according to the mass percentage content of the lithium powder in the lithium supplement layer.
Comparative example 1
The preparation method of the lithium-supplement negative electrode comprises the following steps:
1. lithium supplement slurry
At a humidity of<Under the environment of 1 percent, adding electron conductive agents SP and Al2O3Dissolving the binder PTFE and the inert lithium powder in the NMP solution to form a lithium supplementing slurry with the solid content of 38.2 wt% and the viscosity of 2300mPa ≤;
the lithium supplement slurry comprises the following solids in percentage by mass: conductive agentSP 2.0wt％、Al2O345 wt%, adhesive PTFE 3% and inert lithium powder 50%.
2. Negative electrode active paste
Mixing a silicon-oxygen negative electrode and graphite to prepare a negative electrode material (named as SiO-500) with the specific capacity of 500mAh/g, mixing the SiO-500, a conductive agent SP and a binder according to the mass ratio of 92:4:4, and adding a proper amount of NMP to obtain negative electrode active slurry;
3. lithium-supplementing negative electrode
Coating the cathode active slurry on the upper surface of a Cu foil, drying and rolling to form a cathode active layer, wherein the surface density of the cathode active layer is 6.0mg/cm2The compacted density is 1.5g/cm3；
And coating the lithium supplement slurry on the surface of the negative electrode active layer by adopting a transfer coating method, drying and rolling to obtain the lithium supplement negative electrode.
The lithium powder loading capacity is 0.3mg/cm2。
The method for calculating the lithium powder loading capacity comprises the following steps: and (3) weighing the mass of the pole piece before and after the step (3), calculating the mass of the lithium supplement layer in unit area, and obtaining the loading capacity of the lithium powder in unit area according to the mass percentage content of the lithium powder in the lithium supplement layer.
Test examples
And assembling the negative electrodes of the above examples and comparative examples with the positive electrode and the separator, respectively, and injecting an electrolyte to obtain # 1-11 lithium ion batteries.
The positive electrode comprises a positive electrode active material NCM811, a conductive agent SP and a binder PVDF, wherein the positive electrode active material NCM811, the conductive agent SP and the binder are mixed in a mass ratio of 94: 3: 3;
the electrolyte is 1M LiPF6The solvent is 30 EC: 70EMC, 3% FEC, 1% VC.
The first coulombic efficiency, the capacity retention ratio at 200 weeks and the internal lithium deposition condition of the lithium ion battery 1-11# were measured, and the results are shown in table 1.
1. First coulombic efficiency
And at the temperature of 25 ℃, charging the battery core after liquid injection and standing by using a current of 0.1 ℃ until the cut-off voltage is 4.25V, charging the battery core at a constant voltage until the current is 0.02C, standing for 30min, discharging the battery core at a current of 0.2C until the voltage is 2.7V, and taking the ratio of the discharge capacity to the charge capacity as the first coulombic efficiency of the battery.
2. Capacity retention rate
At 25 ℃, the cell is subjected to charge-discharge test at 0.5C, discharge at 1C and cut-off current of 0.05C, and the ratio of the discharge capacity after 200 weeks to the first discharge capacity is recorded as a retention rate.
3. Internal lithium deposition
And (4) after the lithium ion battery is cycled for 200 weeks, disassembling the lithium ion battery and observing the lithium precipitation condition of the negative electrode.
TABLE 1
Figure BDA0003003038540000151
Figure BDA0003003038540000161
From table 1, it can be seen that:
1. the lithium ion conductive agent is added into the lithium supplement layer, so that the formation of lithium dendrite is inhibited, the improvement of the first coulombic efficiency and the cycle performance is realized, and the lithium supplement effect is excellent;
2. the electronic conductive agent is beneficial to improving the speed of lithium ions inserted into the negative active material, and the inorganic particles are beneficial to promoting the dispersion of lithium powder, so that the electronic conductive agent, the inorganic particles and the lithium ion conductive agent are matched to form a solid product, the lithium supplementing effect can be further optimized, and the formation of lithium dendrites can be inhibited;
3. the lithium powder loading in the lithium supplement layer can affect the electrochemical performance of the battery after pre-lithiation, and excessive lithium powder loading can improve the first coulombic efficiency, but can cause the lithium separation phenomenon, so that the capacity retention rate is reduced after circulation.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The lithium supplement negative electrode is characterized by comprising a negative electrode current collector, a negative electrode active layer arranged on at least one functional surface of the negative electrode current collector and a lithium supplement layer arranged on the surface of the negative electrode active layer;
the lithium supplement layer comprises lithium powder and a lithium ion conductive agent.
2. The lithium compensated negative electrode of claim 1, wherein the lithium ion conductive agent is selected from the group consisting of lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, sulfide solid electrolyte and Li1+xAlxM2－x(PO4)3M is selected from at least one of Ti, Ga, Sc, In, Y and Ge, and x is more than or equal to 0.01 and less than or equal to 1.0.
3. The lithium supplement negative electrode as claimed in claim 1 or 2, wherein the lithium supplement layer contains 15-80% of the lithium powder and 20-85% of the lithium ion conductive agent by mass.
4. The lithium-supplementing negative electrode according to claim 3, wherein the lithium-supplementing layer is configured such that the lithium powder is loaded in an amount of 0.05 to 1.0mg/cm2。
5. The lithium-supplementing negative electrode as claimed in any one of claims 1 to 4, wherein the particle size of the lithium ion conductive agent is 100-2000 nm.
6. The lithium compensated negative electrode of claim 5, wherein the lithium compensation layer further comprises inorganic particles.
7. The lithium replenishment negative electrode of claim 6, wherein the lithium replenishment layer further comprises an electron conducting agent.
8. The lithium replenishment negative electrode of claim 7, wherein the lithium replenishment layer further comprises a binder.
9. The lithium-supplementing negative electrode according to claim 8, wherein the lithium-supplementing layer comprises, by mass: 15-70% of lithium powder, 15-55% of lithium ion conductive agent, 10-30% of inorganic particles, 0.5-4.0% of electronic conductive agent and 1.0-5.0% of binder.
10. A lithium ion battery comprising the lithium-complementary negative electrode according to any one of claims 1 to 9.
CN202110354024.7A 2021-04-01 2021-04-01 Lithium-supplementing negative electrode and application thereof Pending CN113097448A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110354024.7A CN113097448A (en) 2021-04-01 2021-04-01 Lithium-supplementing negative electrode and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110354024.7A CN113097448A (en) 2021-04-01 2021-04-01 Lithium-supplementing negative electrode and application thereof

Publications (1)

Publication Number Publication Date
CN113097448A true CN113097448A (en) 2021-07-09

Family

ID=76672345

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110354024.7A Pending CN113097448A (en) 2021-04-01 2021-04-01 Lithium-supplementing negative electrode and application thereof

Country Status (1)

Country Link
CN (1) CN113097448A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113745480A (en) * 2021-08-28 2021-12-03 河南海宏科技有限公司 Preparation method and application of layered two-dimensional material coated nickel-cobalt-manganese ternary positive electrode material
CN113782823A (en) * 2021-08-12 2021-12-10 浙江锋锂新能源科技有限公司 Preparation method of electrolyte membrane with lithium supplementing function for solid lithium battery
CN114050231A (en) * 2021-11-12 2022-02-15 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery
CN114335428A (en) * 2021-12-30 2022-04-12 重庆冠宇电池有限公司 Positive plate, preparation method and battery
CN114497463A (en) * 2021-12-20 2022-05-13 青岛中科赛锂达新能源技术合伙企业(有限合伙) Method for continuously supplementing lithium to negative electrode of lithium ion battery
CN115241519A (en) * 2022-08-09 2022-10-25 江苏正力新能电池技术有限公司 Lithium ion battery
CN115295864A (en) * 2021-11-09 2022-11-04 深圳市德方创域新能源科技有限公司 Positive electrode lithium supplement additive and preparation method and application thereof
CN115842097A (en) * 2022-07-22 2023-03-24 宁德时代新能源科技股份有限公司 Positive plate, secondary battery, battery module, battery pack and electric device
CN116344745A (en) * 2023-05-30 2023-06-27 江苏正力新能电池技术有限公司 Negative electrode plate, manufacturing method thereof, lithium battery and electric equipment
WO2024073897A1 (en) * 2022-10-08 2024-04-11 宁德时代新能源科技股份有限公司 Negative electrode sheet, secondary battery, and electrical apparatus

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993098A (en) * 2015-06-10 2015-10-21 中航锂电（洛阳）有限公司 Lithium supplement negative electrode piece, preparing method thereof, lithium-ion supercapacitor and lithium-ion battery
CN111244394A (en) * 2020-01-19 2020-06-05 河南电池研究院有限公司 Metal lithium composite electrode and preparation method thereof
CN111613771A (en) * 2020-06-29 2020-09-01 蜂巢能源科技有限公司 Battery cathode and preparation method and application thereof
CN111864181A (en) * 2019-04-25 2020-10-30 中国科学院物理研究所 Pre-lithiated silicon negative electrode and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993098A (en) * 2015-06-10 2015-10-21 中航锂电（洛阳）有限公司 Lithium supplement negative electrode piece, preparing method thereof, lithium-ion supercapacitor and lithium-ion battery
CN111864181A (en) * 2019-04-25 2020-10-30 中国科学院物理研究所 Pre-lithiated silicon negative electrode and preparation method and application thereof
CN111244394A (en) * 2020-01-19 2020-06-05 河南电池研究院有限公司 Metal lithium composite electrode and preparation method thereof
CN111613771A (en) * 2020-06-29 2020-09-01 蜂巢能源科技有限公司 Battery cathode and preparation method and application thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113782823A (en) * 2021-08-12 2021-12-10 浙江锋锂新能源科技有限公司 Preparation method of electrolyte membrane with lithium supplementing function for solid lithium battery
CN113745480A (en) * 2021-08-28 2021-12-03 河南海宏科技有限公司 Preparation method and application of layered two-dimensional material coated nickel-cobalt-manganese ternary positive electrode material
CN115295864A (en) * 2021-11-09 2022-11-04 深圳市德方创域新能源科技有限公司 Positive electrode lithium supplement additive and preparation method and application thereof
CN115295864B (en) * 2021-11-09 2023-08-11 深圳市德方创域新能源科技有限公司 Positive electrode lithium supplementing additive and preparation method and application thereof
CN114050231A (en) * 2021-11-12 2022-02-15 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery
CN114497463A (en) * 2021-12-20 2022-05-13 青岛中科赛锂达新能源技术合伙企业(有限合伙) Method for continuously supplementing lithium to negative electrode of lithium ion battery
CN114335428A (en) * 2021-12-30 2022-04-12 重庆冠宇电池有限公司 Positive plate, preparation method and battery
CN114335428B (en) * 2021-12-30 2024-01-30 重庆冠宇电池有限公司 Positive plate, preparation method and battery
CN115842097A (en) * 2022-07-22 2023-03-24 宁德时代新能源科技股份有限公司 Positive plate, secondary battery, battery module, battery pack and electric device
CN115241519A (en) * 2022-08-09 2022-10-25 江苏正力新能电池技术有限公司 Lithium ion battery
WO2024073897A1 (en) * 2022-10-08 2024-04-11 宁德时代新能源科技股份有限公司 Negative electrode sheet, secondary battery, and electrical apparatus
CN116344745A (en) * 2023-05-30 2023-06-27 江苏正力新能电池技术有限公司 Negative electrode plate, manufacturing method thereof, lithium battery and electric equipment

Similar Documents

Publication Publication Date Title
CN113097448A (en) Lithium-supplementing negative electrode and application thereof
JP5882516B2 (en) Lithium secondary battery
CN110165284B (en) Lithium ion secondary battery
WO2020063371A1 (en) Positive electrode piece and lithium-ion secondary battery
CN101388449B (en) Positive plate of high power lithium ionic cell and lithium ionic cell containing the same
WO2016201942A1 (en) Lithium ion battery having high-rate charge-discharge performance
CN112106233B (en) Positive electrode composition for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery
CN115020678B (en) Positive electrode active material, electrochemical device, and electronic device
WO2011001666A1 (en) Positive electrode for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery
WO2020111201A1 (en) Lithium ion secondary battery positive electrode composition, lithium ion secondary battery positive electrode, and lithium ion secondary battery
CN111557056A (en) Three-dimensional structure electrode and electrochemical device including the same
CN113394370B (en) Electrode plate and battery containing same
CN111834620A (en) Lithium metal battery positive electrode, lithium metal battery and preparation method thereof
CN111162322A (en) Preparation method of low-temperature lithium ion battery
CN114242942A (en) Composite buffer layer with stable negative electrode interface and solid-state lithium metal battery thereof
CN102593416B (en) Lithium secondary battery and cathode plate thereof
JP2012089464A (en) Nonaqueous electrolyte secondary battery and method for manufacturing nonaqueous electrolyte secondary battery
CN113921801B (en) Lithium supplementing material, positive electrode material and lithium ion secondary battery
CN115189014A (en) Preparation and application of composite electrolyte membrane based on sodium ion sulfide solid electrolyte
CN114400321A (en) Low-temperature charge-discharge lithium ion battery and negative electrode material thereof
CN105720265A (en) Carbon nanotube polymer lithium ion battery and preparation method thereof
WO2024016940A1 (en) Positive electrode plate, secondary battery, battery module, battery pack and electric device
CN109346665B (en) Preparation method of lithium ion battery based on negative electrode lithium pre-supplement
KR20240017067A (en) Battery cathode material, manufacturing method thereof, and application thereof
CN203103398U (en) Positive pole piece and battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210709