CN111430684A - Composite negative electrode and preparation method and application thereof - Google Patents

Composite negative electrode and preparation method and application thereof Download PDF

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CN111430684A
CN111430684A CN202010060401.1A CN202010060401A CN111430684A CN 111430684 A CN111430684 A CN 111430684A CN 202010060401 A CN202010060401 A CN 202010060401A CN 111430684 A CN111430684 A CN 111430684A
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negative electrode
metal
lithium
composite
layer
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CN111430684B (en
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陈少杰
黄海强
郑晓醒
秦士林
马忠龙
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Svolt Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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

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Abstract

The invention discloses a composite cathode and a preparation method and application thereof, wherein the composite cathode comprises a metal composite layer and a cathode sheet substrate, wherein the metal composite layer comprises a cathode material layer and metal nano-particles infiltrated into the cathode material layer; the negative electrode piece substrate is provided with a lithium metal layer, and the metal composite layer is attached to the lithium metal layer. The composite negative electrode controls lithium dendrites by utilizing the alloying confinement effect of the metal nanoparticles and lithium ions, delays or inhibits the deposition of the lithium ions on a lithium metal layer, so that the lithium ions are relatively and uniformly deposited, nucleated and grown on each channel, the problems of growth of the lithium dendrites on the surface of the negative electrode and short circuit in the battery caused by nonuniform deposition of the lithium ions are solved, and the cycle performance, the rate capability, the safety performance, the service life and the like of the battery can be obviously improved.

Description

Composite negative electrode and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a composite negative electrode and a preparation method and application thereof.
Background
With the development of electrical equipment in large-scale and multi-functional directions, higher requirements are put on the energy density and service life of lithium ion secondary batteries, and due to the rapid development and wide application of various portable electronic equipment and electric automobiles, the demand on lithium ion batteries with high energy and long cycle life is very urgent. The negative electrode material of the current commercial lithium ion battery is mainly graphite, and due to the low theoretical capacity (372mAh/g) and the poor high-rate charge-discharge performance, the further improvement of the energy of the lithium ion battery is limited. The silicon-carbon material also faces the problems of material pulverization caused by low first charge-discharge efficiency, large expansion, long cycle and the like. To meet the energy density requirements of rechargeable batteries, current research efforts are mainly focused on high specific capacity battery systems, such as: silicon, tin, lithium metal, lithium sulfur batteries, and the like.
Lithium metal has extremely high theoretical specific capacity and low electrochemical potential, and is a very promising negative electrode material. However, it is difficult to apply it to commercial lithium batteries for reasons of safety and efficiency, and in particular, during repeated deposition and dissolution of lithium metal, the uneven deposition of lithium ions causes the inevitable growth of lithium dendrites on the surface of the negative electrode, thereby penetrating the separator to cause internal short-circuiting of the battery; also, the high specific surface area of the lithium dendrite and electrolyte interface promotes the continuous formation of the SEI film, resulting in an increase in internal resistance causing a rapid decrease in coulombic efficiency. Therefore, lithium batteries having high energy density, long cycle life and good safety performance are under further study.
Disclosure of Invention
In view of the above, the present invention is directed to a composite negative electrode, a method for preparing the same, and an application thereof, so as to solve the problems of lithium dendrite growth on the surface of the negative electrode and short circuit in the battery caused by non-uniform deposition of lithium ions, and achieve the purpose of preventing or inhibiting the generation and growth of lithium dendrite, thereby significantly improving the cycle performance, rate capability, safety performance, and service life of the battery.
To achieve the above object, according to a first aspect of the present invention, a composite anode is provided. According to an embodiment of the present invention, the composite anode includes:
the metal composite layer comprises a negative electrode material layer and metal nano-particles infiltrated into the negative electrode material layer;
the negative electrode piece substrate is provided with a lithium metal layer, and the metal composite layer is attached to the lithium metal layer.
Further, the metal nanoparticles are uniformly distributed in the anode material layer.
Further, the anode material layer includes at least one selected from a carbon-based material, a silicon-based material, and a silicon-oxygen-based material.
Further, the metal nanoparticles are at least one selected from the group consisting of silver particles, aluminum particles, magnesium particles, zinc particles, and gold particles.
Further, the metal purity of the metal nanoparticles is 99.99-99.999%.
Further, the total volume of the metal nanoparticles infiltrated into the negative electrode material layer is 5-1000 nm thick.
Further, the thickness of the negative electrode material layer is 10-60 mu m, and the porosity of the negative electrode material layer is 30-55%.
Further, the negative plate substrate comprises a lithium metal layer and a copper metal layer which are attached to each other.
Furthermore, the thickness of the lithium metal layer is 5-50 μm.
Compared with the prior art, the composite negative electrode has at least the following advantages: 1. by permeating metal nano particles into the negative electrode material layer, the metal nano particles can be compounded with negative electrode materials such as graphite, silicon oxide and the like to form a compact and uniform metal composite thin layer. After the metal composite layer is attached to the lithium metal layer of the negative plate substrate to form the composite negative electrode, lithium ions can be alloyed with metal nanoparticles Ag, Mg, Au, Zn, Al and the like in the deposition process and then deposited or permeate into a negative electrode material, and finally deposited on the lithium metal layer with lower potential orderly and slowly, namely, the lithium dendrite can be controlled by utilizing the alloying confinement effect of the metal nanoparticles and the lithium ions, the deposition of the lithium ions on the lithium metal layer is delayed or inhibited, the lithium ions are relatively and uniformly deposited, nucleated and grown on each channel, the internal short circuit caused by the growth of individual overgrowth dendrites is avoided, and the cycle performance of the battery is improved; 2. after the metal composite layer is attached to the lithium metal layer of the negative electrode sheet substrate, part of metal nano particles directly contact with the lithium metal layer and carry out alloying reaction, and a thin alloy layer is formed at the contact position of the metal composite layer and the lithium metal layer, so that the uniform distribution of the surface potential of the negative electrode can be facilitated, lithium ions can be more uniformly deposited in the charging and discharging process, and the formation of lithium dendrites can be further inhibited; 3. even if lithium dendrites are formed on the lithium metal layer, the risk that the lithium dendrites pierce the electrolyte layer can be further reduced due to the existence of the negative electrode material layer; 4. the negative electrode sheet substrate can not only provide low potential and high capacity, but also play a role in lithium supplement, thereby further improving the first effect and capacity of the battery; 5. when the composite cathode is used for preparing a battery, the cycle performance, the rate capability, the safety performance, the service life and the like of the battery can be obviously improved, wherein the first effect of the battery can reach more than 85%, and the capacity retention rate is not lower than 95% after the battery is subjected to charge-discharge cycle for 80 weeks.
Another object of the present invention is to provide a method for preparing the above composite anode, so that the composite anode can significantly improve the cycle performance, safety performance, service life, etc. of a battery.
To achieve the above object, according to a second aspect of the present invention, there is provided a method for producing a composite anode. According to an embodiment of the present invention, the method employs scheme 1 or scheme 2, wherein,
the scheme 1 comprises the following steps: forming a negative electrode material layer on an aluminum foil in advance, transferring the negative electrode material layer to a lithium metal layer of a negative electrode sheet substrate by using the aluminum foil, and then infiltrating metal nanoparticles into the negative electrode material layer by adopting a physical vapor deposition method;
the scheme 2 comprises the following steps: forming a negative electrode material layer on an aluminum foil in advance, enabling metal nano particles to permeate into the negative electrode material layer by adopting a physical vapor deposition method, and transferring a formed metal composite layer to a lithium metal layer of a negative electrode sheet substrate by utilizing the aluminum foil.
Further, in the scheme 1 or the scheme 2, the physical vapor deposition method is performed in a dry environment with a dew point of not higher than-40 ℃.
Further, the physical vapor deposition method is a vacuum evaporation method, an electron beam evaporation method, an ion sputtering method, a magnetron sputtering method, an arc plasma method, or a molecular beam epitaxy method.
Further, the scheme 1 comprises: (1) forming a negative electrode material layer on an aluminum foil and transferring the negative electrode material layer to a lithium metal layer of the negative electrode sheet substrate by using the aluminum foil so as to obtain a composite substrate; (2) and placing the composite matrix on a vacuum chamber substrate table of a vacuum evaporation device in a dry environment with the dew point not higher than minus 40 ℃, heating and uniformly rotating the composite matrix, simultaneously heating and evaporating high-purity metal into an atomic state, and enabling metal atom steam flow to permeate into the negative electrode material layer so as to obtain the composite negative electrode.
Further, in the step (2), the heating temperature is 50-170 ℃, the rotating speed of the uniform rotation is 1-20 r/min, the evaporation rate of the high-purity metal is 0.001-0.3 nm/s, and the vacuum degree of the vacuum chamber is 10-4～10- 6Pa。
Compared with the prior art, the method for preparing the composite negative electrode has at least the following advantages: 1. by adopting a physical vapor deposition method, metal nano particles can be more uniformly and compactly infiltrated into the negative electrode material layer, so that the deposition, nucleation and growth uniformity of lithium ions on each channel can be further improved, internal short circuit caused by growth of individual ultra-long dendritic crystals can be avoided, and the cycle performance of the battery can be better improved; 2. the prepared composite negative electrode can ensure that lithium ions are firstly alloyed with metal nanoparticles such as Ag, Mg, Au, Zn, Al and the like in the deposition process and then deposited or permeate into a negative electrode material, and finally are deposited on a lithium metal layer with lower potential orderly and slowly, namely, lithium dendrites can be controlled by utilizing the alloying limited domain effect of the metal nanoparticles and the lithium ions, the deposition of the lithium ions on the lithium metal layer is delayed or inhibited, the lithium ions are relatively and uniformly deposited, nucleated and grown on each channel, the phenomenon that internal short circuit is generated due to the growth of individual overgrowth dendrites is avoided, and the cycle performance of the battery is favorably improved; 3. after the metal composite layer is attached to the lithium metal layer of the negative electrode sheet substrate, part of metal nano particles directly contact with the lithium metal layer and carry out alloying reaction, and a thin alloy layer is formed at the contact position of the metal composite layer and the lithium metal layer, so that the uniform distribution of the surface potential of the negative electrode can be facilitated, lithium ions can be more uniformly deposited in the charging and discharging process, and the formation of lithium dendrites can be further inhibited; 4. even if lithium dendrites are formed on the lithium metal layer, the risk that the lithium dendrites pierce the electrolyte layer can be further reduced due to the existence of the negative electrode material layer; 5. the negative electrode sheet substrate can not only provide low potential and high capacity, but also play a role in lithium supplement, thereby further improving the first effect and capacity of the battery; 6. the method has simple process and is convenient for industrial production; 7. the prepared composite negative electrode can be used for preparing a battery, the cycle performance, the rate capability, the safety performance, the service life and the like of the battery can be obviously improved, wherein the first efficiency of the battery can be up to more than 85%, and the capacity retention rate is not lower than 95% after the battery is subjected to charge-discharge cycle for 80 weeks.
Another objective of the present invention is to provide a lithium battery to improve the overall performance of the lithium battery. In order to achieve the above object, according to a third aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery has the composite negative electrode or the composite negative electrode obtained by the preparation method. Compared with the prior art, the lithium battery has the advantages of good cycle stability, long cycle life, good rate performance, high safety, long service life and the like, wherein the first efficiency of the battery can reach more than 85%, the capacity retention rate is not lower than 95% after the battery is charged and discharged for 80 weeks, and the lithium battery can be widely applied to the fields of new energy automobiles and the like.
Another object of the present invention is to provide a vehicle to further improve the competitiveness of the vehicle. To achieve the above object, according to a fourth aspect of the present invention, a vehicle is provided, which has the above lithium battery according to an embodiment of the present invention. Compared with the prior art, the vehicle safety is higher, and the service life of the battery is longer.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural view of a composite anode according to an embodiment of the present invention.
Fig. 2 is a schematic structural view of a composite anode according to still another embodiment of the present invention.
Fig. 3 is a schematic view of a method of preparing a composite anode according to one embodiment of the present invention.
Fig. 4 is a graph showing the cycle characteristics of the battery having a composite anode prepared in example 1 of the present invention.
Fig. 5 is a graph showing the cycle characteristics of the battery having a composite anode prepared in example 2 of the present invention.
Fig. 6 is a graph showing the cycle characteristics of the battery having a composite anode prepared in example 3 of the present invention.
Fig. 7 is a graph showing the cycle characteristics of the battery prepared in comparative example 1 according to the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
According to a first aspect of the invention, a composite anode is presented. According to an embodiment of the present invention, as shown in fig. 1, the composite anode includes: the cathode plate comprises a metal composite layer 10 and a cathode plate substrate 20, wherein the metal composite layer 10 comprises a cathode material layer 11 and metal nano-particles 12 penetrating into the cathode material layer 11; the negative electrode sheet substrate 20 has a lithium metal layer 21, and the metal composite layer 10 is bonded to the lithium metal layer 21. According to the composite negative electrode, the metal nanoparticles are infiltrated into the negative electrode material layer, the lithium dendrites are controlled by utilizing the alloying confinement effect of the metal nanoparticles and lithium ions, the deposition of the lithium ions on the lithium metal layer is delayed or inhibited, the lithium ions are relatively and uniformly deposited, nucleated and grown on each channel, the internal short circuit caused by the growth of the individual ultra-long dendrites is avoided, and the cycle performance of the battery is favorably improved. When the composite cathode is used for preparing a battery, the cycle performance, the rate capability, the safety performance, the service life and the like of the battery can be obviously improved, wherein the first effect of the battery can reach more than 85%, and the capacity retention rate is not lower than 95% after the battery is subjected to charge-discharge cycle for 80 weeks.
The composite negative electrode according to the above embodiment of the present invention will be described in detail with reference to fig. 1 to 2.
Metal composite layer 10
According to an embodiment of the present invention, the metal composite layer 10 includes the anode material layer 11 and the metal nanoparticles 12 infiltrated into the anode material layer 11. According to the invention, the metal nanoparticles are infiltrated into the negative electrode material layer, so that the metal nanoparticles and the negative electrode material such as graphite, silicon oxide and the like are compounded to form a compact and uniform metal composite thin layer, and then the metal composite layer is attached to the lithium metal layer of the negative electrode plate substrate to form the composite negative electrode, so that lithium ions are firstly alloyed with the metal nanoparticles in the deposition process and then deposited or infiltrated into the negative electrode material, and finally deposited on the lithium metal layer with lower potential orderly and slowly, and thus the lithium ions can be relatively and uniformly deposited, nucleated and grown on each channel, internal short circuit caused by growth of individual ultra-long dendritic crystals is avoided, and the cycle performance of the battery is favorably improved; furthermore, after the metal composite layer is attached to the lithium metal layer of the negative electrode sheet substrate, part of the metal nanoparticles directly contact with the lithium metal layer and undergo an alloying reaction, and a thin alloy layer is formed at the contact position of the metal composite layer and the lithium metal layer, so that the uniform distribution of the surface potential of the negative electrode can be facilitated, lithium ions can be deposited more uniformly in the charging and discharging process, and the formation of lithium dendrites can be further inhibited.
According to an embodiment of the present invention, the metal nanoparticles 12 may be uniformly distributed in the anode material layer 11, thereby allowing lithium ions to be more uniformly deposited, nucleated and grown on each passage from the anode material layer to the lithium metal layer, and further avoiding the problem of internal short circuit due to the growth of individual ultra-long dendrites.
According to still another embodiment of the present invention, the anode material layer 11 may include at least one selected from a carbon-based material, a silicon-based material, and a silicon-oxygen-based material, and for example, the anode material layer may be a graphite layer, a single crystal silicon layer, a silicon oxide layer, or a composite layer of graphite, single crystal silicon, and silicon oxide in any ratio, etc., thereby facilitating not only the improvement of the cycle performance of the battery but also the infiltration of atomic metal particles.
According to another embodiment of the present invention, the metal nanoparticles 12 may be at least one selected from silver particles, aluminum particles, magnesium particles, zinc particles and gold particles, and the inventors found that the above metal nanoparticles can further improve the alloying reaction activity and confinement effect of the metal nanoparticles and lithium ions, so as to further facilitate delaying or inhibiting the deposition of lithium ions on the lithium metal layer, so that the lithium ions are relatively uniformly deposited, nucleated and grown on each channel, and avoid causing internal short circuit due to the growth of individual ultra-long dendrites, thereby further improving the cycle performance of the battery. Further, the metal purity of the metal nanoparticles 12 can be 99.99-99.999%, so that the influence of impurities on the alloying confinement effect of the metal nanoparticles and lithium ions can be effectively avoided, and the generation of lithium dendrites and the growth of individual ultra-long lithium dendrites can be further inhibited.
According to another embodiment of the invention, the total volume of the metal nanoparticles 12 penetrating into the negative electrode material layer 11 can be 5-1000 nm thick, so that enough metal nanoparticles can be ensured in the negative electrode material layer, and the metal composite layer can be ensured to have a long-acting and stable alloying confinement effect, thereby further facilitating to delay or inhibit the deposition of lithium ions on the lithium metal layer, and achieving the effects of inhibiting the generation of lithium dendrites and the growth of individual ultra-long lithium dendrites, and improving the safety performance and cycle performance of the battery. Further, the thickness of the negative electrode material layer 11 may be 10 to 60 μm, for example, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or 55 μm, and thus, the alloying confinement effect of the metal composite layer on lithium ions may be further ensured, and the safety performance, cycle performance, rate capability, and service life of the battery may be further improved.
According to still another embodiment of the present invention, the porosity of the negative electrode material layer 11 may be 30 to 55%, for example, 30%, 33%, 36%, 39%, 42%, 45%, 48%, 51%, or 55%. The inventor finds that by controlling the porosity of the negative electrode material layer 11, the infiltration of metal nanoparticles is facilitated, and the total infiltration amount of the metal nanoparticles can be controlled to be the volume of the negative electrode material layer 11 with the thickness of 5-1000 nm, so that a uniform and compact metal composite layer is facilitated to be formed, the alloying limited domain effect of the metal composite layer on lithium ions can be effectively guaranteed, and the safety performance, the cycle performance, the rate capability and the service life of the battery are obviously improved.
Negative plate substrate 20
According to the embodiment of the present invention, the negative electrode sheet substrate 20 has the lithium metal layer 21, and the metal composite layer 10 is attached to the lithium metal layer 21. After the metal composite layer is attached to the lithium metal layer of the negative electrode sheet substrate, partial metal nanoparticles directly contact with the lithium metal layer and carry out alloying reaction, and a thin alloy layer is formed at the contact position of the metal composite layer and the lithium metal layer, so that the uniform distribution of the surface potential of the negative electrode can be facilitated, lithium ions can be more uniformly deposited in the charging and discharging process, and the formation of lithium dendrites can be further inhibited; in addition, the negative electrode sheet substrate with the lithium metal layer can not only provide low potential and high capacity for the battery, but also play a role in lithium supplement, so that the first effect and the capacity of the battery can be further improved.
According to an embodiment of the present invention, the negative electrode sheet substrate 20 may be a lithium metal substrate, as shown in fig. 2, or may include a lithium metal layer 21 and a copper metal layer 22 attached to each other, for example, the negative electrode sheet substrate 20 may be a lithium foil or an L i-Cu composite tape having a lithium foil and a copper foil, further, the lithium metal layer 21 may have a thickness of 5 to 50 μm, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm, and thus the amount of pre-lithium of the negative electrode sheet may be effectively adjusted, so as to reduce volume expansion and facilitate improvement of battery cycle performance.
In summary, the composite negative electrode of the above embodiments of the present invention has at least the following advantages: 1. by permeating metal nano particles into the negative electrode material layer, the metal nano particles can be compounded with negative electrode materials such as graphite, silicon oxide and the like to form a compact and uniform metal composite thin layer. After the metal composite layer is attached to the lithium metal layer of the negative plate substrate to form the composite negative electrode, lithium ions can be alloyed with metal nanoparticles Ag, Mg, Au, Zn, Al and the like in the deposition process and then deposited or permeate into a negative electrode material, and finally deposited on the lithium metal layer with lower potential orderly and slowly, namely, the lithium dendrite can be controlled by utilizing the alloying confinement effect of the metal nanoparticles and the lithium ions, the deposition of the lithium ions on the lithium metal layer is delayed or inhibited, the lithium ions are relatively and uniformly deposited, nucleated and grown on each channel, the internal short circuit caused by the growth of individual overgrowth dendrites is avoided, and the cycle performance of the battery is improved; 2. after the metal composite layer is attached to the lithium metal layer of the negative electrode sheet substrate, part of metal nano particles directly contact with the lithium metal layer and carry out alloying reaction, and a thin alloy layer is formed at the contact position of the metal composite layer and the lithium metal layer, so that the uniform distribution of the surface potential of the negative electrode can be facilitated, lithium ions can be more uniformly deposited in the charging and discharging process, and the formation of lithium dendrites can be further inhibited; 3. even if lithium dendrites are formed on the lithium metal layer, the risk that the lithium dendrites pierce the electrolyte layer can be further reduced due to the existence of the negative electrode material layer; 4. the negative electrode sheet substrate can not only provide low potential and high capacity, but also play a role in lithium supplement, thereby further improving the first effect and capacity of the battery; 5. when the composite cathode is used for preparing a battery, the cycle performance, the rate capability, the safety performance, the service life and the like of the battery can be obviously improved, wherein the first effect of the battery can reach more than 85%, and the capacity retention rate is not lower than 95% after the battery is subjected to charge-discharge cycle for 80 weeks.
According to a second aspect of the invention, a method of making a composite anode is provided. According to an embodiment of the present invention, the method employs scheme 1 or scheme 2, wherein, as shown in fig. 3, scheme 1 comprises: forming a negative electrode material layer on an aluminum foil in advance, transferring the negative electrode material layer to a lithium metal layer of a negative electrode sheet substrate by using the aluminum foil, and then infiltrating metal nano particles into the negative electrode material layer by adopting a physical vapor deposition method; the scheme 2 comprises the following steps: and then transferring the formed metal composite layer to a lithium metal layer of the negative electrode sheet substrate by using the aluminum foil. The method is simple in process, and the prepared composite cathode can be used for a battery, so that the cycle performance, the rate capability, the safety performance, the service life and the like of the battery can be remarkably improved, wherein the first efficiency of the battery can reach more than 85%, and the capacity retention rate is not lower than 95% after the battery is charged and discharged for 80 weeks.
According to an embodiment of the present invention, in the embodiment 1 or the embodiment 2, the physical vapor deposition method is performed in a dry environment having a dew point of not higher than-40 ℃, thereby ensuring that the lithium metal layer of the negative electrode sheet substrate does not react with moisture in the air.
According to another embodiment of the present invention, the type of the physical vapor deposition method used in preparing the metal composite layer is not particularly limited, and those skilled in the art can select the method according to actual needs, for example, vacuum evaporation, electron beam evaporation, ion sputtering, magnetron sputtering, arc plasma method, or molecular beam epitaxy, so that the metal nanoparticles can be more favorably and uniformly infiltrated into the negative electrode material layer to form a uniform and dense metal composite layer.
According to still another embodiment of the present invention, the preparing of the composite anode according to scheme 1 may include: (1) forming a negative electrode material layer on the aluminum foil and transferring the negative electrode material layer to the lithium metal layer of the negative electrode sheet substrate by using the aluminum foil so as to obtain a composite substrate; (2) and placing the composite matrix on a vacuum chamber substrate table of a vacuum evaporation device in a dry environment with the dew point not higher than minus 40 ℃, heating and uniformly rotating the composite matrix, simultaneously heating and evaporating high-purity metal into an atomic state, and enabling metal atom steam flow to permeate into a negative electrode material layer so as to obtain the composite negative electrode. Therefore, the metal nano particles can be more uniformly infiltrated into the negative electrode material layer and are compounded with the negative electrode material such as graphite, silicon oxide and the like to obtain a compact and uniform metal composite layer, so that lithium ions can be more favorably and uniformly deposited, nucleated and grown on each channel of the metal composite layer, and internal short circuit caused by growth of individual ultra-long dendritic crystals is avoided.
According to another embodiment of the present invention, in the step (2), the heating temperature may be 50 to 170 ℃, the rotation speed of the uniform rotation may be 1 to 20 rpm, the evaporation rate of the high-purity metal may be 0.001 to 0.3nm/s, and the vacuum degree of the vacuum chamber may be 10-4～10-6Pa, the inventor finds that by controlling the process conditions, the rate of alloying reaction of the metal nanoparticles and the lithium ions can be obviously improved, the uniformity of the metal composite layer can be further improved, any other impurities are avoided from being introduced, and the purity of the metal nanoparticles is ensured, so that the generation of lithium dendrites and the growth of individual ultra-long lithium dendrites can be further inhibited, and the safety performance, the cycle performance, the rate capability and the service life of the battery can be obviously improved. Note that the evaporation rate refers to a speed at which the metal nanoparticles penetrate into the anode material layer.
According to another embodiment of the present invention, the metal nanoparticles may be at least one selected from silver particles, aluminum particles, magnesium particles, zinc particles and gold particles, and the inventors found that the above metal nanoparticles may be selected to further improve the alloying reaction activity and confinement effect of the metal nanoparticles and lithium ions, so as to further facilitate delaying or inhibiting the deposition of lithium ions on the lithium metal layer, so that the lithium ions are relatively uniformly deposited, nucleated and grown on each channel, and avoid causing internal short circuit due to the growth of individual ultra-long dendrites, thereby further improving the cycle performance of the battery. Furthermore, the metal purity of the metal nanoparticles can be 99.99-99.999%, so that the alloying confinement effect of the metal nanoparticles and lithium ions can be effectively avoided from being influenced due to the existence of impurities, and the generation of lithium dendrites and the growth of individual ultra-long lithium dendrites can be further inhibited.
According to still another embodiment of the present invention, the anode material layer may include at least one selected from a carbon-based material, a silicon-based material, and a silicon-oxygen-based material, and for example, the anode material layer may be a graphite layer, a single crystal silicon layer, a silicon oxide layer, or a composite layer of graphite, single crystal silicon, and silicon oxide formed in any ratio, and the like, thereby facilitating not only the improvement of the cycle performance of the battery but also the infiltration of atomic metal particles.
According to another embodiment of the invention, the total volume of the metal nanoparticles penetrating into the negative electrode material layer can be 5-1000 nm thick, and the thickness of the negative electrode material layer can be 10-60 μm, so that the alloying confinement effect of the metal composite layer on lithium ions can be further ensured, and the safety performance, the cycle performance, the rate capability and the service life of the battery can be further improved.
According to another embodiment of the present invention, the negative electrode sheet substrate 20 may be a lithium metal substrate, as shown in fig. 2, or may include a lithium metal layer 21 and a copper metal layer 22 attached to each other, for example, the negative electrode sheet substrate 20 may be a lithium foil or an L i-Cu composite tape having a lithium foil and a copper foil, further, the thickness of the lithium metal layer 21 may be 5 to 50 μm, so that the amount of pre-lithium of the negative electrode sheet may be effectively adjusted, thereby reducing volume expansion and facilitating improvement of battery cycle performance.
In summary, the method for preparing the composite negative electrode according to the above embodiment of the present invention has at least the following advantages: 1. by adopting a physical vapor deposition method, metal nano particles can be more uniformly and compactly infiltrated into the negative electrode material layer, so that the deposition, nucleation and growth uniformity of lithium ions on each channel can be further improved, internal short circuit caused by growth of individual ultra-long dendritic crystals can be avoided, and the cycle performance of the battery can be better improved; 2. the prepared composite negative electrode can ensure that lithium ions are firstly alloyed with metal nanoparticles such as Ag, Mg, Au, Zn, Al and the like in the deposition process and then deposited or permeate into a negative electrode material, and finally are deposited on a lithium metal layer with lower potential orderly and slowly, namely, lithium dendrites can be controlled by utilizing the alloying limited domain effect of the metal nanoparticles and the lithium ions, the deposition of the lithium ions on the lithium metal layer is delayed or inhibited, the lithium ions are relatively and uniformly deposited, nucleated and grown on each channel, the phenomenon that internal short circuit is generated due to the growth of individual overgrowth dendrites is avoided, and the cycle performance of the battery is favorably improved; 3. after the metal composite layer is attached to the lithium metal layer of the negative electrode sheet substrate, part of metal nano particles directly contact with the lithium metal layer and carry out alloying reaction, and a thin alloy layer is formed at the contact position of the metal composite layer and the lithium metal layer, so that the uniform distribution of the surface potential of the negative electrode can be facilitated, lithium ions can be more uniformly deposited in the charging and discharging process, and the formation of lithium dendrites can be further inhibited; 4. even if lithium dendrites are formed on the lithium metal layer, the risk that the lithium dendrites pierce the electrolyte layer can be further reduced due to the existence of the negative electrode material layer; 5. the negative electrode sheet substrate can not only provide low potential and high capacity, but also play a role in lithium supplement, thereby further improving the first effect and capacity of the battery; 6. the method has simple process and is convenient for industrial production; 7. the prepared composite negative electrode can be used for preparing a battery, the cycle performance, the rate capability, the safety performance, the service life and the like of the battery can be obviously improved, wherein the first efficiency of the battery can be up to more than 85%, and the capacity retention rate is not lower than 95% after the battery is subjected to charge-discharge cycle for 80 weeks. It should be noted that the features and effects described above for the composite negative electrode are also applicable to the method for preparing the composite negative electrode, and are not described in detail here.
According to a third aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery has the composite negative electrode or the composite negative electrode obtained by the preparation method. The lithium battery has the advantages of good cycle stability, long cycle life, good rate performance, high safety, long service life and the like, wherein the first effect of the battery can reach more than 85%, the capacity retention rate is not lower than 95% after the battery is subjected to charge-discharge cycle for 80 weeks, and the lithium battery can be widely applied to the fields of new energy automobiles and the like.
According to an embodiment of the invention, the lithium battery can be an all-solid-state battery, so that the energy density of the lithium battery can be further improved, wherein a high-purity metal material can be infiltrated into a graphite/L i/Cu composite matrix, a silicon/L i/Cu composite matrix or a silicon oxide/L i/Cu composite matrix through vacuum evaporation or sputtering and the like to form a composite cathode with dense and uniform distribution, and the prepared composite cathode is assembled with a positive plate and a solid electrolyte layer to obtain the all-solid-state lithium battery.
It should be noted that the features and effects described above for the composite negative electrode and the method for preparing the composite negative electrode are also applicable to the lithium battery, and are not described in detail herein.
According to a fourth aspect of the invention, the invention proposes a vehicle having the above-described lithium battery according to an embodiment of the invention. The vehicle has higher safety and longer service life of the battery. It should be noted that the features and effects described above for the lithium battery are also applicable to the vehicle, and are not described in detail here.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Transferring the silicon-coated aluminum foil to a copper-lithium composite belt in a drying room environment with the dew point of less than-40 ℃, cutting the copper-lithium composite belt into square pieces of 10 × 10mm, fixing the square pieces on a stainless steel evaporation substrate plate by using an adhesive tape, placing the composite substrate piece in a vacuum chamber of evaporation equipment, placing a tungsten boat containing 5g of pure magnesium at the position of an evaporation source, and vacuumizing until the vacuum degree reaches 5.0 × 10-4Regulating the heating temperature of the substrate to 100 ℃, the rotation speed of the substrate to 8 r/min, controlling the evaporation rate to be 0.01nm/s by regulating the current applied to the tungsten boat, continuously evaporating while keeping the evaporation rate stable until the evaporation thickness is 300nm on a film thickness instrument, stopping evaporation, reducing the heating temperature of the substrate to room temperature, opening an air valve to restore the vacuum chamber to normal pressure, opening a cabin door to take out the negative electrode material of magnesium metal evaporated on the substrate plate, respectively punching the evaporated magnesium-silicon negative electrode material into wafers with the diameter of 10mm, and mixing the wafer with the NCM622 positive electrode material and L i6P5And (3) performing charge and discharge tests after the Cl electrolyte membrane is assembled into the all-solid-state lithium battery, and displaying the results: under the charging and discharging conditions of 70 ℃ and 0.1C/0.1C, the first effect reaches 84.4%, and after the first effect is continuously cycled for 125 weeks under the charging and discharging conditions of 0.1C/0.1C, the capacity retention rate reaches 94.2%, as shown in FIG. 4.
Example 2
Transferring the carbon-coated aluminum foil to a copper-lithium composite belt in a drying room environment with the dew point of less than-40 ℃, cutting the copper-lithium composite belt into square pieces of 10 × 10mm, fixing the square pieces on a stainless steel evaporation substrate plate by using an adhesive tape, placing the composite substrate piece in a vacuum chamber of evaporation equipment, placing a tungsten boat containing 5g of pure silver at the position of an evaporation source, and vacuumizing until the vacuum degree reaches 5.0 × 10-4Adjusting the heating temperature of the substrate to 100 ℃, the rotation speed of the substrate to 8 r/min, controlling the evaporation rate to be 0.01nm/s by adjusting the current applied to the tungsten boat, continuously evaporating under the condition of keeping the evaporation rate stable until the evaporation thickness is 400nm displayed on a film thickness instrument, stopping evaporation, reducing the heating temperature of the substrate to room temperature, opening an air valve to restore the vacuum chamber to normal pressure, opening a cabin door to take out the negative electrode material of silver metal evaporated on the substrate plate, respectively punching the evaporated silver-carbon negative electrode material into wafers with the diameter of 10mm, and mixing the wafers with the NCM622 positive electrode material and L i positive electrode material6P5And (3) performing charge and discharge tests after the Cl electrolyte membrane is assembled into the all-solid-state lithium battery, and displaying the results: the first effect reaches 89.75% under the charging and discharging conditions of 70 ℃ and 0.1C/0.1C; the whole charge-discharge cycle process is as follows: performing 1-2 charge-discharge cycles under the charge-discharge condition of 0.1C/0.1C, performing 20-30 charge-discharge cycles under the charge-discharge condition of 0.3C/0.3C, and repeatingThis operation was repeated a plurality of times, and the capacity retention rate reached 95.4% after 83 weeks of the cycle, as shown in fig. 5.
Example 3
Transferring the carbon-coated aluminum foil to a copper-lithium composite belt in a drying room environment with the dew point of less than-40 ℃, cutting the copper-lithium composite belt into square pieces of 10 × 10mm, fixing the square pieces on a stainless steel evaporation substrate plate by using an adhesive tape, placing the composite substrate piece in a vacuum chamber of evaporation equipment, placing a tungsten boat containing 5g of pure gold at the position of an evaporation source, and vacuumizing until the vacuum degree reaches 3.0 × 10-4Regulating the heating temperature of the substrate to 100 ℃, the rotation speed of the substrate to 10 r/min, controlling the evaporation rate to be 0.01nm/s by regulating the current applied to the tungsten boat, continuously evaporating while keeping the evaporation rate stable until the evaporation thickness is 500nm on a film thickness instrument, stopping evaporation, reducing the heating temperature of the substrate to room temperature, opening an air valve to restore the vacuum chamber to normal pressure, opening a cabin door to take out the negative electrode material of the evaporated lithium metal on the substrate plate, respectively punching the evaporated gold-carbon negative electrode material into wafers with the diameter of 10mm, and mixing the wafers with the NCM622 positive electrode material and L i6P5And (3) performing charge and discharge tests after the Cl electrolyte membrane is assembled into the all-solid-state lithium battery, and displaying the results: the first effect is 87.84% under the charging and discharging conditions of 70 ℃ and 0.1C/0.1C; the whole charge-discharge cycle process is as follows: the operation is repeated for 2 charge and discharge cycles under the charge and discharge condition of 0.1C/0.1C, and then 20 to 30 charge and discharge cycles under the charge and discharge condition of 0.3C/0.3C, and the capacity retention rate reaches 95.4 percent after 83 weeks of cycle, which is shown in FIG. 6.
Comparative example 1
NCM622 positive electrode Material, L i6P5The Cl electrolyte membrane and the graphite cathode are assembled into a die battery with the diameter of 10mm, and a charge-discharge test is carried out under the charge-discharge conditions of 70 ℃ and 0.1C/0.1C, and the result shows that: the first effect was 72.9%, and the capacity retention remained only 72% after 100 weeks of cycling, as shown in fig. 7.
Results and conclusions:
as can be seen from fig. 4 to 7, compared with comparative example 1, the battery prepared by using the composite negative electrode of the embodiment of the present invention has stable cycle performance and coulombic efficiency, and the first efficiency of the battery is high; as seen from fig. 2 and fig. 3, after 20 to 30 charge-discharge cycles are performed under the charge-discharge condition of 0.3C/0.3C, 1 to 2 charge-discharge cycles are performed under the charge-discharge condition of 0.1C/0.1C, and this is repeated many times, the change of the discharge specific capacity of the battery is not large, and the coulombic efficiency is stable, which indicates that the battery prepared by using the composite negative electrode of the above embodiment of the present invention has better rate capability.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A composite anode, comprising:
the metal composite layer comprises a negative electrode material layer and metal nano-particles infiltrated into the negative electrode material layer;
the negative electrode piece substrate is provided with a lithium metal layer, and the metal composite layer is attached to the lithium metal layer.
2. The composite anode according to claim 1, wherein the metal nanoparticles are uniformly distributed in the anode material layer,
optionally, the anode material layer includes at least one selected from a carbon-based material, a silicon-based material, and a silicon-oxygen-based material,
optionally, the metal nanoparticles are at least one selected from the group consisting of silver particles, aluminum particles, magnesium particles, zinc particles, and gold particles,
optionally, the metal purity of the metal nanoparticles is 99.99-99.999%.
3. The composite negative electrode according to claim 1 or 2, wherein the total volume of the metal nanoparticles infiltrated into the negative electrode material layer is 5 to 1000nm in thickness,
optionally, the thickness of the negative electrode material layer is 10-60 μm, and the porosity of the negative electrode material layer is 30-55%.
4. The composite negative electrode according to claim 1, wherein the negative electrode sheet substrate comprises a lithium metal layer and a copper metal layer attached to each other,
optionally, the thickness of the lithium metal layer is 5-50 μm.
5. A method of preparing the composite anode according to any one of claims 1 to 4, characterized by employing scheme 1 or scheme 2, wherein,
the scheme 1 comprises the following steps: forming a negative electrode material layer on an aluminum foil in advance, transferring the negative electrode material layer to a lithium metal layer of a negative electrode sheet substrate by using the aluminum foil, and then infiltrating metal nanoparticles into the negative electrode material layer by adopting a physical vapor deposition method;
the scheme 2 comprises the following steps: forming a negative electrode material layer on an aluminum foil in advance, enabling metal nano particles to permeate into the negative electrode material layer by adopting a physical vapor deposition method, and transferring a formed metal composite layer to a lithium metal layer of a negative electrode sheet substrate by utilizing the aluminum foil.
6. The method according to claim 5, wherein the physical vapor deposition method in the scheme 1 or the scheme 2 is performed in a dry environment having a dew point of not higher than-40 ℃,
optionally, the physical vapor deposition method is vacuum evaporation, electron beam evaporation, ion sputtering, magnetron sputtering, arc plasma, or molecular beam epitaxy.
7. The method according to claim 5 or 6, wherein the scheme 1 comprises:
(1) forming a negative electrode material layer on an aluminum foil and transferring the negative electrode material layer to a lithium metal layer of the negative electrode sheet substrate by using the aluminum foil so as to obtain a composite substrate;
(2) and placing the composite matrix on a vacuum chamber substrate table of a vacuum evaporation device in a dry environment with the dew point not higher than minus 40 ℃, heating and uniformly rotating the composite matrix, simultaneously heating and evaporating high-purity metal into an atomic state, and enabling metal atom steam flow to permeate into the negative electrode material layer so as to obtain the composite negative electrode.
8. The method according to claim 7, wherein in the step (2), the heating temperature is 50-170 ℃, the rotation speed of the uniform rotation is 1-20 rpm, the evaporation rate of the high-purity metal is 0.001-0.3 nm/s, and the vacuum degree of the vacuum chamber is 10-4～10-6Pa。
9. A lithium battery comprising the composite negative electrode according to any one of claims 1 to 4 or the composite negative electrode produced by the method according to any one of claims 5 to 8.
10. A vehicle characterized by having the lithium battery of claim 9.
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