CN114512674A - Negative pole piece and metal lithium battery - Google Patents

Negative pole piece and metal lithium battery Download PDF

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Publication number
CN114512674A
CN114512674A CN202011279926.0A CN202011279926A CN114512674A CN 114512674 A CN114512674 A CN 114512674A CN 202011279926 A CN202011279926 A CN 202011279926A CN 114512674 A CN114512674 A CN 114512674A
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lithium
structure layer
porous structure
current collector
negative electrode
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张柯
郭姿珠
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BYD Co Ltd
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BYD 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The application discloses a negative pole piece and a metal lithium battery, wherein the negative pole piece comprises a current collector and a porous structure layer arranged on at least one surface of the current collector; wherein the electronic conductivity of the porous structure layer gradually decreases in a direction away from the current collector. This application is through adopting electronic conductivity to reduce porous structure layer step by step along keeping away from the mass flow body direction for lithium ion can be deposited in the porous structure layer near the mass flow body in advance, thereby realizes the purpose of guide lithium ion deposit, has avoided the uneven formation of lithium dendrite that brings of lithium ion deposit, improves metal lithium battery's energy density and cycle life.

Description

Negative pole piece and metal lithium battery
Technical Field
The application generally relates to the technical field of batteries, in particular to a negative pole piece and a metal lithium battery.
Background
Compared with the traditional electrode, the lithium metal cathode has higher theoretical specific capacity and lower electrochemical potential, and can obviously improve the mass energy density of the existing battery system. However, when the existing lithium metal negative electrode is subjected to charge-discharge cycle, lithium dendrite is easily formed due to uneven deposition of lithium ions on the surface of the lithium metal, so that the battery is short-circuited to cause the safety problem of the battery; in addition, the high electrochemical reactivity of the lithium metal makes the lithium metal easily react with the electrolyte to generate an SEI (solid electrolyte interface) film, and the change of the volume of the lithium metal negative electrode in the battery cycle can cause the SEI film generated on the surface of the negative electrode to be broken to expose the fresh lithium metal surface, so that the lithium metal negative electrode further reacts with the electrolyte to consume active lithium, and the cycle life of the lithium metal battery is influenced.
Disclosure of Invention
In view of the above-mentioned drawbacks and deficiencies of the prior art, it is desirable to provide a negative electrode plate and a lithium metal battery.
As a first aspect of the present application, the present application provides a negative electrode tab.
Preferably, the negative electrode sheet includes:
the current collector comprises a current collector and a porous structure layer arranged on at least one surface of the current collector;
wherein the electronic conductivity of the porous structure layer gradually decreases in a direction away from the current collector.
Preferably, the porous structure layer is formed by stacking n sublayers, each sublayer has micropores, and the electronic conductivity inside each sublayer is uniformly distributed; wherein n is an integer of 2-10; preferably, n is an integer of 2 to 3.
Preferably, each of said sublayers is formed of a different porous material having a different electronic conductivity; or the like, or a combination thereof,
each of said sublayers being formed of the same porous material having a different degree of oxidation or reduction; or the like, or, alternatively,
each of the sub-layers is formed by compounding a plurality of porous materials having different electron conductivities, wherein the electron conductivity distribution between the sub-layers is different by changing the mass ratio of the high electron conductivity component to the low electron conductivity component in the porous material.
Preferably, the porous material is selected from at least one of a carbon-based material, a silicon-based material, a high molecular polymer, a metal nanowire material, and a metal material having a pore structure;
wherein the carbon-based material is selected from at least one of graphene, porous carbon, carbon nanotubes and carbon fibers; the silicon-based material is selected from at least one of silicon, silicon nanowire, silicon dioxide and silicon monoxide; the metal nanowire material is selected from at least one of copper nanowires, silver nanowires and gold nanowires; the metal material having a pore structure is selected from at least one of copper, aluminum, and nickel.
Preferably, the thickness of the sub-layer is 100nm-50 μm, and the thickness of the porous structure layer is less than or equal to 100 μm.
Preferably, the pore diameters of the micropores of the different sub-layers are the same or different, and the pore diameters of the micropores are less than or equal to 500 mu m.
Preferably, the porous structure layer is filled with metal lithium, and the metal lithium is simple substance lithium and/or lithium powder.
Preferably, the porous structure layer is further filled with a lithium-philic material, and the lithium-philic material is selected from LiNO3Zinc oxide, copper nanoparticles, silicon nanoparticles.
Preferably, the current collector is selected from copper foil, titanium foil, nickel foil, iron foil or tin foil.
As a second aspect of the present application, there is provided a lithium metal battery.
Preferably, the lithium metal battery comprises the negative electrode sheet according to the first aspect.
The beneficial effect of this application:
this application is through adopting electronic conductivity to reduce porous structure layer step by step along keeping away from the mass flow body direction for lithium ion can be deposited in the porous structure layer near the mass flow body in advance, thereby realizes the purpose of guide lithium ion deposit, has avoided the uneven formation of lithium dendrite that brings of lithium ion deposit, improves metal lithium battery's energy density and cycle life.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
fig. 1 is a structural side view of a negative electrode tab according to an embodiment of the present application;
fig. 2 is a scanning electron microscope image of a porous structure layer according to an embodiment of the present disclosure.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
It is noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the description of the present application, the terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
Unless otherwise specified, all raw materials referred to in the present application are commercially available raw materials.
According to a first aspect of the present application, please refer to fig. 1, which illustrates a negative electrode tab of a preferred embodiment of the present application, including: the current collector comprises a current collector 1 and a porous structure layer 2 arranged on at least one surface of the current collector 1; wherein the electronic conductivity of the porous structure layer 2 gradually decreases in a direction away from the current collector 1.
In the present embodiment, the current collector 1 is a conductive substrate commonly used in the art for collecting current, and the porous structure layer 2 is equivalent to a functional layer compounded on the current collector 1, wherein the surface of the porous structure layer 2 far away from the current collector 1 is close to a battery separator.
When the negative pole piece is used as the negative pole of the metal lithium battery, the metal lithium embedded into the negative pole piece can be provided by the positive pole of the battery during first charging; based on an electrochemical stripping-deposition reaction mechanism generated by the metal lithium negative electrode, in the subsequent charging process of the battery, lithium ions are transported from an electrolyte side to a negative electrode side, electrons are obtained on the surface of the metal lithium, and the metal lithium is deposited in the form of metal-lithium particles; in the discharging process, the metallic lithium is oxidized into lithium ions to be dissolved out into the electrolyte; the porous structure layer 2 with the electronic conductivity gradually reduced in the thickness direction of the current collector body 1 is arranged on the current collector 1, and because the electronic conductivity of the porous structure layer 2 close to the current collector 1 is highest, and the ohmic overpotential at the position during charging is lower, the actual negative electrode potential applied at the position is relatively lower, and the nucleation driving force of lithium ions is maximum, so that the lithium ions are easier to nucleate, the lithium ions can be induced to preferentially deposit on the porous structure layer close to the current collector 1, the lithium ions are prevented from preferentially depositing on the surface of the porous structure layer 2 far away from the current collector 1, and along with the charging process of a battery, the lithium ions are gradually deposited in the porous structure layer 2 from the direction close to the current collector 1 to the direction far away from the current collector 1 due to the existing ohmic overpotential gradient; the method can avoid that lithium ions are preferentially deposited on the surface of the porous structure layer 2 far away from the current collector 1 to form a large amount of surface lithium dendrites after the battery is cycled for a few times, so that the side reaction between the metal lithium and the electrolyte is accelerated, and the service life of the battery is short; moreover, the situation that lithium ions are deposited on the surface of the porous structure layer 2 far away from the current collector 1 preferentially and then block the lower space of the porous structure layer, so that the whole negative pole piece cannot be filled with lithium can be avoided; therefore, the negative pole piece can obviously relieve the formation of lithium dendrites within a period of time or a charge-discharge cycle, inhibit the negative pole from obviously expanding due to the growth of the lithium dendrites, prolong the cycle life of the metal lithium negative pole, enable the deposition of lithium ions in the negative pole to be uniform and compact, obviously improve the space utilization rate of the negative pole and optimize the multiplying power performance of the battery;
wherein, the porous structure layer 2 is equivalently divided into a plurality of regions in the thickness direction thereof, and the regions closer to the current collector 1 have higher electronic conductivity; the porous structure layer 2 preferably has a random 3D pore structure, and a space is reserved for lithium deposition and stripping, during the lithium deposition or extraction, lithium ions can be easily transferred into the porous structure layer 2 or transferred out of the porous structure layer 2, and since the electronic conductivity of the porous structure layer 2 is distributed in a regular manner that the electronic conductivity gradually decreases along the direction away from the current collector 1, metal lithium tends to grow in the porous structure layer close to the current collector 1 and gradually fills the pore structure of the entire porous structure layer 2; moreover, due to the overlarge specific surface area of the porous structure layer 2, the cathode has higher area capacity, the rate capability and the service life of the cathode can be obviously improved; in addition, the pore structure of the porous structure layer can inhibit the large volume change of the metal lithium negative electrode in the charging and discharging process and increase the stable cycle capacity of the metal lithium negative electrode; on the other hand, enough space can be provided for electrolyte permeation, and the performance of the metal lithium battery applying the negative electrode is improved from the aspects;
the porous structure layer may be located on one surface or both surfaces of the current collector 1, so as to form a negative electrode sheet having a single-sided structure or a double-sided structure.
Further, in some preferred embodiments of the present application, the electronic conductivity of the porous structure layer 2 is decreased in a gradient in a direction perpendicular to a normal line of the current collector 1.
Further, in some preferred embodiments of the present application, the porous structure layer 2 is composed of a stack of n sublayers, each of the sublayers has micropores and the electronic conductivity inside each of the sublayers is uniformly distributed; wherein n is an integer of 2-10.
Specifically, the porous structure layer 2 is composed of a stack of n sublayers, wherein the electron conductivity of the ith sublayer is gradually decreased by the first layer adjacent to the current collector 1, so as to have n gradients of electron conductivity distribution in a direction away from the current collector 1, wherein i is an integer from 1 to n. The gradient reduction described in this application should be understood in a broad sense, and the difference value of the electronic conductivity between two adjacent sub-layers from the first layer to the nth layer may be equal or unequal, and when the difference value is unequal, the electronic conductivity may be reduced by multiple times or reduced irregularly by multiple times from the first layer to the nth layer.
The number of sublayers can be adjusted according to the actual requirements of the battery, and the energy density of the negative pole piece, the expected cycle number of the metal lithium battery applying the negative pole piece, the volume of the battery and the like need to be comprehensively considered, so that the cycle life of the negative pole is prolonged, and the waste of the internal space of the battery is avoided.
In some more preferred embodiments, n is an integer of 2 to 3, i.e., the porous structure layer of the negative electrode sheet of the present embodiment is composed of 2 sublayers or 3 sublayers, thereby having an electron conductivity distribution of 2 or 3 gradients in a direction away from the current collector 1.
It is understood that the porous structure layer 2 may exhibit different electron conductivity distributions by changing the stacking manner of the sub-layers having different electron conductivities, such as an increase in gradient, a decrease in periodic gradient, an increase in periodic gradient, a sudden change in non-uniformity, and the like in a direction away from the current collector 1, so as to meet different requirements.
Further, in some preferred embodiments of the present application, each of the sublayers is formed of a different porous material having a different electronic conductivity; or the like, or, alternatively,
each of said sublayers being formed of the same porous material having a different degree of oxidation or reduction; or the like, or, alternatively,
each of the sub-layers is formed by compounding a plurality of porous materials having different electron conductivities, wherein the electron conductivity distribution between the sub-layers is different by changing the mass ratio of the high electron conductivity component to the low electron conductivity component in the porous material.
In the present embodiment, the porous material is defined as a material having a three-dimensional structure and pores existing inside the three-dimensional structure.
Wherein, when the sub-layers are formed using different porous materials, respectively, the 1 st sub-layer 21 is formed of, for example, a1Formed of a porous material, the 2 nd sublayer 22 being formed of a2Porous material, and so on, the nth sublayer being formed of anFormed of a porous material a1The electronic conductivity of the porous material is more than a2，a2Has an electron conductivity of more than an(ii) a Wherein the 1 st sublayer 21 is provided adjacent to the current collector 1The nth sublayer is arranged at the end far away from the current collector 1 in the direction perpendicular to the length direction of the current collector 1 from the 1 st sublayer, so that a gradually reduced electronic conductivity gradient is formed between the 1 st sublayer and the nth sublayer;
wherein, when the sub-layers are formed using the same porous material, respectively, the electronic conductivity of the porous material used to form each sub-layer can be changed by changing the degree of oxidation or reduction of the porous material, so that an electronic conductivity gradient is formed between the sub-layers; wherein the higher the oxidation degree of a certain porous material, such as a porous carbon material, the lower the electronic conductivity thereof; the higher the degree of reduction of a certain porous material, such as an oxidizing porous carbon material, the higher the electron conductivity thereof;
wherein, when a combination of two or more porous materials is respectively employed to form each of the sub-layers, an electron conductivity gradient can be formed between the sub-layers by adjusting the mass ratio of the component having high electron conductivity and the component having low electron conductivity among the plurality of porous materials forming each of the sub-layers.
Further, in some preferred embodiments of the present application, the porous material is formed of at least one selected from the group consisting of a carbon-based material, a silicon-based material, a high molecular polymer, a metal nanowire material, and a metal material having a pore structure;
the metal material having a pore structure is a material obtained by forming pores in a metal body made of metal and having a sheet shape, a block shape, or another suitable shape by using a suitable method such as chemical or laser etching.
Further, in some preferred embodiments of the present application, the carbon-based material is selected from at least one of graphene, porous carbon, carbon nanotubes, and carbon fibers; the porous carbon comprises activated carbon; as shown in fig. 2, the porous structure layer formed of graphene has a significant porous structure.
The silicon-based material is selected from at least one of silicon, silicon nanowire, silicon dioxide and silicon monoxide;
the high molecular polymer is selected from at least one of polyaniline, polyethylene oxide, polyimide, polyacrylic acid, polyethylene, polypropylene, polyacrylonitrile, polystyrene, polyvinyl fluoride, polyether ketone, polyester, polyvinylidene chloride, polytetrafluoroethylene and polyethylene terephthalate;
the metal nanowire material is selected from at least one of copper nanowires, silver nanowires and gold nanowires;
the metal material having a pore structure is selected from at least one of copper, aluminum, and nickel;
the material has good conductivity and stability, and can form a stable porous structure layer framework;
taking carbon-based materials such as graphene and porous carbon as examples, the electrical conductivity of the carbon-based materials depends on the ratio of sp2 hybridized carbon atoms to sp3 hybridized carbon atoms in the structures, the sp2 hybridized carbon atoms have electrical conductivity, and the sp3 hybridized carbon atoms do not have electrical conductivity, so that the electronic conductivity of the carbon-based materials can be changed by adjusting the ratio of sp2 hybridized structures to sp3 hybridized structures in the structures; wherein the proportion of sp2 and sp3 hybrid structures can be achieved by varying the degree of oxidation and the degree of reduction of the carbon-based material; for example, in the case of graphene, the oxidation degree can be increased and the electronic conductivity can be reduced by introducing an oxidation functional group such as carboxyl, carbonyl, hydroxyl and the like to increase the proportion of sp3 hybridized carbon atoms on the surface; the introduction of the oxidizing functional group can be achieved by oxidation treatment of the graphene with an oxidizing agent for a suitable time, exemplary oxidizing agents include nitric acid, sulfuric acid, potassium permanganate, and the like;
similarly, when a carbon-based material having a large number of oxidized functional groups on the surface thereof such as graphene oxide is used, the electronic conductivity of graphene oxide can be changed by treating graphene oxide with a reducing agent for an appropriate time to selectively control the degree of reduction thereof; exemplary reducing agents include unsymmetrical dimethylhydrazine, ascorbic acid, and the like; wherein, the method for changing the oxidation degree or the reduction degree of the carbon-based material can also be realized by heating or microwave and the like;
in preparing each sub-layer, the porous material may be dispersed in a suitable solvent or medium to form a homogeneous dispersion, which may then be applied to a plate or vessel and cooled or filtered to form a hydrogel film.
Further, in some preferred embodiments of the present application, the thickness of the sub-layer is 100nm to 50 μm, and the thickness of the porous structure layer is 100 μm or less.
The thickness of the sub-layer affects the thickness of the porous structure layer, the thickness of the porous structure layer affects the deposition effect of lithium ions and the stability of the porous framework, a stable network structure is not formed when the thickness is too small, the thickness of the negative pole piece is too large when the thickness is too large, the weight of the battery is increased, and the cost of consumed materials is increased; wherein, the thickness of each sub-layer can be the same or different.
Further, in some preferred embodiments of the present application, the pore size of the micropores of the different sublayers is the same or different, the pore size of said micropores being ≦ 500 μm.
The aperture is too low to provide enough accommodation space for lithium ions, so that the rate performance of the negative pole piece is low, and the volume energy density of the battery is too low; too high pore size can result in unstable structure of the porous structure layer, which is easily collapsed and damaged during the preparation process or the circulation process.
The pore diameter of the porous structure layer can be adjusted by regulating and controlling the pore diameter of each sub-layer micropore, so that the magnification performance of the negative pole piece is optimized, and lithium ions are guaranteed to be preferentially deposited on the porous structure layer 2 close to the current collector 1 under relatively large polarization current;
the pore size can be adjusted by means of a pore size control solution, wherein the pore size control solution is a mixed solution composed of more than two reagents with different boiling points, one or more of the reagents can be selectively volatilized under proper temperature treatment, and the other one or more reagents are continuously retained in the micropores, so that the pore size of the micropores is changed. One of the selectable aperture control methods is: the water in the hydrogel membrane is exchanged by adopting the aperture control solution, and partial non-volatile reagents still exist in the micropores of the hydrogel membrane through drying or freeze drying treatment, so that the partial structure of the original micropores is reserved, and the aperture size of the micropores is changed. Exemplary pore size controlling solutions include deionized water and acetone mixed solution, acetone and dimethyl carbonate mixed solution, N-dimethylformamide and dimethyl carbonate mixed solution, solution containing one or more inorganic salts and dispersible low boiling point solvent thereof, suspension, emulsion, such as lithium nitrate and acetone mixed solution, lithium chloride and acetone mixed solution, lithium nitrate and N, N-dimethylformamide mixed solution, and the like, and may also include any ionic liquid and volatile solvent mixed solution.
On one hand, the smaller the pore size of the sub-layer closer to the current collector is, the smaller the ion flow closer to the current collector is, the smaller the pore size of the required micropores is, and the space utilization rate can be increased; on the other hand, providing a smaller pore size for the sub-layer closer to the current collector body can result in a higher electron conductivity for the sub-layer closer to the current collector body, thereby directing lithium ions to preferentially begin deposition in the sub-layer closer to the current collector.
Further, in some preferred embodiments of the present application, metallic lithium is filled in the porous structure layer, and the metallic lithium is elemental lithium and/or lithium powder.
In the embodiment, the filling of the metal lithium in the porous structure layer 2 can be regarded as depositing lithium in advance in the negative electrode plate, that is, supplementing lithium, and the filled metal lithium is used as an active component of the metal lithium negative electrode to stably participate in battery cycle, so that the metal lithium can be used as a lithium deposition site during charging, and can also compensate for the consumption of the active lithium in the battery cycle, and the battery cycle efficiency is improved; in this mode, lithium powder refers to powdery particles having a protective layer formed of, for example, lithium carbonate, lithium fluoride, lithium metasilicate, lithium orthosilicate, lithium phosphate, lithium sulfate, LiTi on the surface of elemental lithium2(PO4)3、Li14Zn(GeO4)4、Li7La3Zr2O12The lithium ion battery is formed by coating materials such as paraffin, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene oxide, polysiloxane, polyacrylonitrile, polypropylene carbonate, polymethyl methacrylate, polyvinyl chloride and the like, plays a role in protecting elemental lithium coated inside the protective layer, and the protective layer is broken to release the elemental lithium when the lithium powder is used;
wherein, the metal lithium can be absorbed into the porous structure layer 2 by capillary action in a molten state, and the porous structure layer 2 provides a stable framework for the deposition and extraction of the metal lithium, so that the volume change caused by the metal lithium during the circulation period is obviously reduced; the filling amount of the metal lithium is 0.5-10 times of the positive electrode capacity of the battery, the filling amount can ensure good cycle performance of the battery, and the whole porous structure layer 2 is not completely filled while the porous structure layer 2 is filled, so that the infiltration of subsequent electrolyte to a negative electrode plate is facilitated;
alternatively, the method of filling metallic lithium may adopt the following two ways:
the first is a melt process: the current collector stacked with the porous structure layer 2 and the metal lithium are subjected to high-temperature treatment together, the metal lithium is melted into flowable liquid at high temperature, and the metal lithium is absorbed in the porous structure layer 2 by utilizing the siphon action;
the second is electrochemical deposition: electrochemical deposition of lithium metal in the porous structure layer 2 may be performed using the assembled half-cell, typically with a lithium sheet as the counter electrode and the corresponding current collector stacked with the porous structure layer 2 as the working electrode.
Further, in some preferred embodiments of the present application, a lithium-philic material for providing nucleation sites to facilitate lithium deposition is further distributed in the porous structure layer, and the lithium-philic material is selected from LiNO3Zinc oxide, copper nanoparticles, silicon nanoparticles.
The lithium-philic material can induce the nucleation of lithium ions, so that the effective specific surface area of the negative pole piece is fully utilized in the lithium deposition process, and the lithium deposition without dendrites and the long cycle life are realized; wherein the addition amount of the lithium-philic material is not more than 10% of the total mass of the porous material forming the porous structure layer.
Further, in some preferred embodiments of the present application, the current collector is a metal foil commonly used in the art, including but not limited to copper foil, titanium foil, nickel foil, iron foil or tin foil.
The preparation method of the negative pole piece can comprise the following steps:
preparing sublayers with different electronic conductivities, wherein each sublayer has micropores and the electronic conductivity in each sublayer is uniformly distributed;
stacking and fixing the sublayers on at least one surface of a current collector in an order that the electronic conductivity is gradually reduced along a direction far away from the current collector;
in this embodiment, the sub-layer may be fixed on the current collector by hot pressing, suction filtration or bonding with an adhesive; when hot pressing or suction filtration is adopted, firstly, the sublayers are stacked on the current collector according to the sequence that the electronic conductivity gradually decreases along the direction far away from the current collector, and then the current collector stacked with the sublayers is subjected to hot pressing or suction filtration, so that each sublayer is fixed on the current collector, wherein the temperature of the hot pressing treatment can be 80-150 ℃, and the pressure can be 0.5-2.0 MPa; when the adhesive is used for bonding, after the first sub-layer is bonded and fixed on the current collector, the second sub-layer is stacked and bonded on the first sub-layer, and the like, until the negative pole piece with the porous structure layer with the proper thickness is obtained.
More specific preparation process can be as follows:
first, a 1 st sublayer is prepared, the 1 st sublayer having an electronic conductivity σ1；
Preparation of the 2 nd sublayer, the electronic conductivity of the 2 nd sublayer being σ2；
By analogy, an ith sublayer is prepared, and the electronic conductivity of the ith sublayer is sigmai；
Until the preparation of the n-th sublayer, the electronic conductivity of which is σn；
Wherein σ1>σ2>…>σi>…>σn
Wherein n is an integer greater than or equal to 2, preferably an integer of 2-10, and more preferably 2 or 3;
wherein each sublayer has micropores;
sequentially overlapping the 1 st to n th layers on at least one surface of the current collector body according to a normal direction perpendicular to the current collector body to form a porous structure layer comprising n sub-layers on at least one surface of the current collector body;
and carrying out high-temperature and high-pressure hot-pressing treatment on the current collector body on which the porous structure layer is superposed so as to compactly connect the sub-layers to obtain the negative pole piece.
Further, before the sub-layers with different electronic conductivities are obtained and the sub-layer stacking is carried out, the step of adjusting the pore size of the micropores of each sub-layer is also included, specifically, the pore size of the micropores of each sub-layer can be adjusted by the pore size control liquid after each sub-layer is prepared into a hydrogel membrane, so as to obtain porous structure layers with the same or different pore size distributions.
Further, the method further comprises a step of filling metal lithium in the micropores after obtaining the negative electrode plate, wherein the manner of filling metal lithium in the micropores can adopt the melting method or the electrochemical deposition method as described above, so as to realize the loading or filling of metal lithium in the porous structure layer.
According to a second aspect of the present application, there is provided a lithium metal battery comprising a negative electrode tab as described above.
In some modes, the lithium metal battery can be an all-solid-state battery, which comprises a negative electrode plate and a positive electrode plate; in other embodiments, the lithium metal battery of the present application may be a semi-solid battery or a liquid battery, which includes a negative electrode plate, a positive electrode plate, a separator located between the negative electrode plate and the positive electrode plate, and an electrolyte.
Illustratively, the positive electrode plate comprises a positive electrode current collector and a positive electrode material layer arranged on the positive electrode current collector; the positive electrode material layer comprises a positive electrode active substance, a conductive agent, a bonding agent and the like, and the positive electrode plate is manufactured by the existing preparation method, for example, slurry containing the positive electrode active substance, the conductive agent, the bonding agent and a solvent is coated on a positive electrode current collector, and the positive electrode plate is dried and then subjected to rolling treatment under 0-5 MPa; wherein the positive electrode current collector may be, but not limited to, a metal foil or the like (e.g., an aluminum foil or the like), and the positive electrodeThe active substance is selected from LiCoO2、LiNiO2、LiCoxNi1-xO2(0≤x≤1)、LiCoxNi1-x-yAlyO2(0≤x≤1，0≤y≤1)、LiMn2O4、LiFexMnyMzO4(M is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, x is 0-1, y is 0-1, z is 0-1, and x + y + z is 1), Li1+xL1－y－zMyNzO2(L, M, N is at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, -x is more than or equal to 0.1 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y + z is more than or equal to 0 and less than or equal to 1), LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4And metal sulfides and oxides such as V2S3、FeS、FeS2、LiMSx(M is at least one of transition metal elements such as Fe, Ni, Cu, Mo and the like, and x is more than or equal to 1 and less than or equal to 2.5), TiO2、Cr3O8、V2O5、MnO2Etc., preferably the particle size of the positive electrode particles is in the range of 100nm to 500 μm; wherein, the binder is a binder commonly used for the positive electrode, and comprises but is not limited to one or more of fluorine-containing resin and polyolefin compounds such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE) and Styrene Butadiene Rubber (SBR); the conductive agent is a common positive electrode conductive agent, such as acetylene black, carbon nanotubes, carbon fibers, carbon black and the like; wherein, the solvent can be one or more selected from N-methylpyrrolidone (NMP), water, ethanol and acetone; wherein, the content of the adhesive is 0.01 to 10wt percent, preferably 0.02 to 5wt percent based on the weight of the positive active material layer; the content of the conductive agent is 0.1-20 wt%, preferably 1-10 wt%; the solvent is generally used in an amount of 50 to 400 wt%.
Illustratively, the electrolyte comprises a solvent and a lithium salt, wherein the solvent has one or more of the following groups: ether group, nitrile group, cyanoester group, fluorineEster groups, tetrazolyl groups, fluorosulfonyl groups, chlorosulfonyl groups, nitro groups, carbonate groups, dicarbonate groups, nitrate groups, fluoroamido groups, diketo groups, azole groups, and triazine groups; the lithium salt is LiPF6、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2And LiN (C)4F9SO2)(CF3SO3) One or more of (a).
Illustratively, when the lithium metal battery of the present application is a semi-solid battery or a liquid battery, the separator may be selected from polyethylene, polypropylene, polyvinylidene fluoride, and a multi-layered composite film of polyethylene, polypropylene, polyvinylidene fluoride.
Illustratively, the metal lithium battery is also provided with a package on the outer side, and the package can be an aluminum plastic film, a stainless steel cylinder, a square aluminum shell and the like.
The metal lithium battery can be a button cell battery or a laminated battery, a full battery or a half battery; the specific preparation method of the lithium metal battery is not particularly limited, and is a preparation method of a conventional lithium metal battery in the field.
Example 1
Preparation of negative pole piece
Mixing 1g of graphene oxide and 0.2g of unsymmetrical dimethylhydrazine, dissolving the mixture in 800ml of distilled water under a stirring state, performing ultrasonic dispersion for 20min, adding 0.2g of 35 mass percent aqueous ammonia into the mixed solution, adjusting the pH value to 7-9, and performing water bath reaction at 100 ℃ for 120 min;
naturally cooling the dispersion liquid to room temperature, and filtering to obtain a graphene oxide hydrogel film;
soaking the graphene oxide hydrogel film in a 10% lithium nitrate aqueous solution by mass for 12 hours, and replacing water in the hydrogel with a lithium nitrate solution containing 10% by mass; then drying at 100 ℃ for 24 hours to obtain a 1 st sub-layer prepared by reducing graphene oxide, wherein the electronic conductivity of the 1 st sub-layer is determined to be 3.6 multiplied by 104S/cm, average pore diameter of 6nm and thickness of 10 μm;
the second sublayer 2 was prepared similarly to the first sublayer 1 except that the water bath reaction time was 60min, and the electron conductivity of the second sublayer 2 was determined to be 1.6X 103S/cm, average pore diameter of 6nm and thickness of 10 μm;
the sub-layer 3 was prepared similarly to the sub-layer 1 except that the water bath reaction time was 30min, the electronic conductivity of the sub-layer 3 was determined to be 370S/cm, the average pore size was 6nm, and the thickness was 10 μm;
the above-mentioned water bath heating time determines the reduced degree and the number of defects of the graphene, and the longer the time is, the higher the reduced degree is, and the higher the electronic conductivity is.
Sequentially placing the 1 st sublayer, the 2 nd sublayer and the 3 rd sublayer on a copper foil, and then carrying out hot pressing at 100 ℃ and under 0.8MPa to obtain a negative pole piece which is arranged in the sequence of the copper foil, the 1 st sublayer, the 2 nd sublayer and the 3 rd sublayer and has an electronic conductivity gradient and is of a composite structure; wherein the thickness of the copper foil is 5 μm;
then heating the obtained negative pole piece and lithium powder to 200 ℃ to control the surface capacity of the metal lithium to 5mAh/cm2And cutting the lithium into 480mm (length) multiplied by 45mm (width) after the lithium is completely blended into the porous structure layer and cooled to room temperature to be used as a negative pole piece for later use.
Preparation of (II) positive pole piece
8.8g LiCoO2Adding a positive electrode active substance (88 wt%), 0.3g of adhesive PVDF (3 wt%), 0.2g of acetylene black (2 wt%) and 0.2g of conductive agent carbon nano tube (2 wt%) into 15g of solvent NMP (N-methyl pyrrolidone), and stirring in a stirrer to form stable and uniform positive electrode slurry;
the positive electrode slurry is evenly and intermittently coated on two sides of an aluminum foil (the size of the aluminum foil is 45mm in width, 480mm in length and 16 mu m in thickness), then dried at 393K, and pressed by a roller press to obtain a positive electrode plate for later use.
Preparation of CEA metal lithium full cell
And (3) in a glove box, aligning the negative pole piece obtained in the step (I) and the positive pole piece obtained in the step (II) and placing the negative pole piece and the positive pole piece in an aluminum-plastic film, inserting a layer of diaphragm (PE) in the middle, injecting 4M DME electrolyte in an injection amount of 3g/Ah, and then vacuumizing and sealing the aluminum-plastic film to obtain the metal lithium full cell.
Example 2
A metal lithium battery is prepared according to the method of the embodiment 1, and the difference is that the preparation of a negative pole piece is different;
the negative electrode plate of the embodiment is prepared as follows:
dissolving 1g of graphene in 800mL of distilled water, performing ultrasonic dispersion for 20min, and performing water bath reaction at 100 ℃ for 120 min;
naturally cooling the dispersion liquid to room temperature, and filtering to obtain a graphene oxide hydrogel film;
soaking the graphene oxide hydrogel film in a 10% lithium nitrate aqueous solution by mass for 12 hours, and replacing water in the hydrogel with a lithium nitrate solution containing 10% by mass; freeze-drying with liquid nitrogen and a freeze-dryer gave a 1 st sublayer of three-dimensional network prepared from graphene, the 1 st sublayer having an electronic conductivity of 2.06 x 10 as determined2S/cm, average pore diameter of about 5 μm, and thickness of about 20 μm;
taking 300ml of 1mol/L HCl aqueous solution, adding 3g of polyaniline aqueous solution with the mass fraction of 10% and 0.3g of graphene, uniformly stirring, taking out, standing at room temperature, filtering and drying to obtain a 2 nd sub-layer, wherein the electron conductivity of the 2 nd sub-layer is 2.29S/cm, the average pore diameter is 10 mu m, and the thickness is about 35 mu m;
sequentially placing the 1 st sublayer and the 2 nd sublayer on a copper foil, and then carrying out hot pressing at 80 ℃ and 0.5MPa to obtain a negative pole piece which is arranged in sequence of the copper foil, the 1 st sublayer and the 2 nd sublayer and has an electronic conductivity gradient and is of a composite structure; wherein the thickness of the copper foil is 5 μm;
then heating the obtained negative pole piece and lithium powder to 200 ℃ to control the surface capacity of the metal lithium to 5mAh/cm2And cutting the lithium into 480mm (length) multiplied by 45mm (width) after the lithium is completely blended into the porous structure layer and cooled to room temperature to be used as a negative pole piece for later use.
Comparative example 1
A metal lithium battery is prepared according to the method of the embodiment 1, except that the negative pole piece is different, and the negative pole piece of the comparative example is prepared as follows:
depositing a lithium metal simple substance with the thickness of 25 microns on a copper foil, and cutting the lithium metal simple substance into 480mm (length) multiplied by 45mm (width) to be used as a negative pole piece; wherein the copper foil has a thickness of 5 μm.
Comparative example 2
A metal lithium battery is prepared according to the method of the embodiment 2, and the difference is that the negative pole piece is different; the negative pole piece of the comparative example is prepared as follows:
placing the 1 st sublayer prepared in the example 1 on a copper foil, and then carrying out hot pressing to obtain a negative pole piece with a copper foil-1 st sublayer and a composite structure; wherein the thickness of the copper foil is 5 μm;
then heating the obtained negative pole piece and lithium powder to 200 ℃ to control the surface capacity of the metal lithium to 5mAh/cm2And cutting the lithium into 480mm (length) multiplied by 45mm (width) as a negative pole piece after the lithium is completely blended into the first sublayer and cooled to room temperature.
Battery performance testing
(I) Battery cycle Performance test
The lithium metal batteries obtained in the above examples and comparative examples were subjected to a cycle performance test by the following method:
the batteries prepared in the examples and the comparative examples are respectively 20, and the batteries are subjected to charge-discharge cycle test at 0.5C under the conditions of 298 +/-1K on a LAND CT2001C secondary battery performance detection device, and the steps are as follows: standing for 10 min; constant current charging is carried out until 4.4V is cut off; standing for 10 min; discharging to 3V with constant current, namely 1 cycle. Repeating the step, wherein when the battery capacity is lower than 80% of the first discharge capacity in the circulation process, the circulation is terminated, the circulation times are the circulation life of the battery, and each group is averaged;
(II) measurement of expansion change in thickness of negative electrode plate
The batteries prepared in each example and comparative example were subjected to a charge-discharge cycle test at 0.5C under 298 ± 1K, according to the following procedure: standing for 10 min; constant current charging is carried out until 4.4V is cut off; standing for 10 min; discharging to 3V with constant current, namely 1 cycle. The step is repeated, the battery is disassembled after 1000 times of circulation, and the negative pole piece of the battery is taken out. The negative pole piece is cut to expose the cross section, the cross section is polished by an ion cutting machine, and the change of the thickness of the negative pole piece is measured by a micrometer screw.
The results of the experiments are shown in the following table:
Figure BDA0002780420470000151
Figure BDA0002780420470000161
it can be seen from the cycle performance test of the battery that the battery of the example shows more excellent cycle performance than the comparative example, which shows that the negative electrode sheet of the present application has better cycle life.
The cathode pole piece of the comparative example 2 has the same electronic conductivity at each position of the porous structure layer, so that the overpotential acting on the electrode surface by the whole porous structure layer is the same, the original power of lithium ions deposited in the porous structure layer is the same, the lithium ions near the diaphragm are richer, the lithium ions have lower nucleation energy on the surface of the porous structure layer near the diaphragm, and the lithium ions are preferentially deposited on the surface of the porous structure layer near the diaphragm to form lithium dendrites; the growth of lithium dendrites is self-enhancing, and once formed, new lithium ions are more prone to deposit at the lithium dendrites, thus exacerbating the formation of lithium dendrites; in addition, the metal lithium has larger volume change in the charging and discharging processes, the change of the thickness of the metal lithium causes the movement of a metal lithium interface, in the large volume change process, SEI is broken to expose a new metal lithium surface, lithium ions are more prone to be deposited on the surface, and the generation of lithium dendrites is also accelerated; on one hand, the continuous growth of the lithium dendrite can pierce through a diaphragm to cause short circuit inside the metal lithium battery and thermal runaway explosion; on the other hand, the lithium dendrite is cracked to form dead lithium in the dissolution process, so that the capacity of the negative electrode is reduced, and the cycle life of the battery is influenced in multiple aspects;
this application makes lithium ion can be in the porous structure layer of being close to the mass flow body deposit in priority through the porous structure layer that adopts electron conductivity to go up the gradient reduction in the vertical direction of keeping away from the mass flow body to realize the lithium deposit of no lithium dendrite in a period or in the charge-discharge cycle period, with this cycle life who has improved metal lithium cell.
The thickness measurement of the battery negative pole piece after 1000 times of circulation shows that the thickness of the negative pole piece in the embodiment 1 and the embodiment 2 is not obviously increased compared with the thickness of the pole piece before circulation (namely the thickness of the initial pole piece), the surface of the pole piece after circulation is relatively flat and smooth, and a compact structure is still kept, while the thickness of the negative pole piece in the comparative example 1 and the comparative example 2 is obviously increased compared with the thickness of the initial pole piece, and a large amount of irregular sediments are observed on the surface of the pole piece.
The foregoing description is only exemplary of the preferred embodiments of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.

Claims (10)

1. A negative electrode sheet, comprising:
the current collector comprises a current collector and a porous structure layer arranged on at least one surface of the current collector;
wherein the electronic conductivity of the porous structure layer gradually decreases in a direction away from the current collector.
2. The negative electrode sheet of claim 1, wherein the porous structure layer is formed by stacking n sublayers, each sublayer has micropores, and the electronic conductivity inside each sublayer is uniformly distributed; wherein n is an integer of 2-10; preferably, n is an integer of 2 to 3.
3. The negative electrode tab of claim 2, wherein each of the sublayers are formed of different porous materials having different electronic conductivities; or the like, or, alternatively,
each of said sublayers being formed of the same porous material having a different degree of oxidation or reduction; or the like, or, alternatively,
each of the sub-layers is formed by compounding a plurality of porous materials having different electron conductivities, wherein the electron conductivity distribution between the sub-layers is different by changing the mass ratio of the high electron conductivity component to the low electron conductivity component in the porous material.
4. The negative electrode plate as claimed in claim 3, wherein the porous material is selected from at least one of carbon-based material, silicon-based material, high molecular polymer, metal nanowire material and metal material having a pore structure.
5. The negative electrode sheet of claim 4, wherein the carbon-based material is selected from at least one of graphene, porous carbon, carbon nanotube and carbon fiber; the silicon-based material is selected from at least one of silicon, silicon nanowire, silicon dioxide and silicon monoxide; the metal nanowire material is selected from at least one of copper nanowires, silver nanowires and gold nanowires; the metal material having a pore structure is selected from at least one of copper, aluminum, and nickel.
6. The negative electrode plate as claimed in claim 2, wherein the thickness of the sub-layer is 100nm to 50 μm, and the thickness of the porous structure layer is less than or equal to 100 μm.
7. The negative electrode plate as claimed in claim 2, wherein the pore diameters of the micropores of the different sub-layers are the same or different, and the pore diameter of the micropores is less than or equal to 500 μm.
8. The negative electrode plate as claimed in claim 1, wherein the porous structure layer is filled with metallic lithium, and the metallic lithium is elemental lithium and/or lithium powder.
9. The negative electrode sheet of claim 1, wherein the porous structure layer is further filled with a lithium-philic material selected from LiNO3Zinc oxide, copper nanoparticles, silicon nanoparticles.
10. A lithium metal battery comprising the negative electrode sheet according to any one of claims 1 to 9.
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