CN115842103A - Negative pole piece and preparation method thereof - Google Patents
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- CN115842103A CN115842103A CN202111290725.5A CN202111290725A CN115842103A CN 115842103 A CN115842103 A CN 115842103A CN 202111290725 A CN202111290725 A CN 202111290725A CN 115842103 A CN115842103 A CN 115842103A
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a negative pole piece, negative pole piece includes: a negative electrode active material layer; an inner layer film covering the negative electrode active material layer; and an outer layer film covering the inner layer film, wherein the negative electrode active material layer comprises graphite, the inner layer film comprises at least 10 metal organic compound monolayers, and the outer layer film comprises at least 40 organic polymer monolayers.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to a negative electrode and a preparation method thereof.
Background
Metallic lithium has the lowest electrode potential (lithium has the lowest electrode potential standard hydrogen electrode) and an ultra-high theoretical specific capacity (3860 mAh electrode polarity) -1 ) And is an attractive cathode material for next-generation high-energy-density batteries. However, the problems of unlimited volume effect, lithium dendrite and the like exist, which cause the problems of low coulombic efficiency, poor cycle performance and safety for the first time, and the practical application of the lithium dendrite is severely restricted. Graphite has a small volume effect (volume change) as a current mainstream negative electrode material of a commercial lithium secondary battery<10%), better cycle performance, low cost, etc., however, the gram capacity of the catalyst gradually approaches to the limit value and cannot meet the requirements of people on the limit valueHigh specific energy and practical requirements for fast-charging batteries.
Therefore, there is a need in the art for a negative electrode plate that combines the advantages of high specific capacity of lithium metal and high stability of graphite, and can overcome the problems of volume effect and dendritic growth of lithium during the cycling process, so as to improve the specific capacity, safety and cycling stability of the lithium secondary battery.
Disclosure of Invention
In view of the above problems, an object of the present application is to provide a negative electrode sheet and a method for manufacturing the same, wherein a film having high mechanical strength, high flexibility and being lithium-philic is covered on the surface of the negative electrode sheet. In the process of charging the battery, the lithium-philic film can guide metal lithium to be uniformly nucleated and deposited at the interface of the inner layer film/the negative electrode active material layer, and a graphite/lithium metal composite negative electrode is formed in situ, so that a mixed working mode of reversible insertion/extraction of lithium ions and deposition/stripping of the metal lithium is realized, and the specific capacity of the negative electrode active material and the integral energy density of the secondary battery are improved. In addition, the film has high mechanical strength and good flexibility, can relieve the volume effect of lithium metal while inhibiting the growth of lithium dendrites, maintains the stability of the structure of the negative pole piece, and improves the cycle life and the safety of the secondary battery. Meanwhile, graphite is used as a carrier for lithium metal deposition, and the volume effect of the lithium metal is relieved to a certain extent.
This application first aspect provides a negative pole piece, negative pole piece includes:
a negative electrode active material layer;
an inner layer film covering the negative electrode active material layer; and
an outer layer film covering the inner layer,
wherein the negative electrode active material layer includes graphite, the inner layer film includes at least 10 monolayers of a metal organic compound, and the outer layer film includes at least 40 monolayers of an organic polymer.
The inner layer film/outer layer film covered on the surface of the negative electrode active material layer is a double-layer structure with uniform and controllable composition and structure, and can be prepared by a molecular layer deposition method. The outer layer film is composed of an organic polymer with electronic insulation and good flexibility, such as polyurea, so that the side reaction of a negative electrode active material and an electrolyte interface can be reduced, meanwhile, the volume change of a negative electrode in a circulation process is relieved, the structural stability of the negative electrode is maintained, and the circulation life of the battery is prolonged. The inner film is composed of a high mechanical strength and lithium philic metal organic polymer such as Zincone. The metal organic polymer contains lithium-philic metal sites such as a zinc simple substance, and the metal sites can preferentially react with lithium ions to generate an M-Li alloy, reduce the nucleation overpotential of lithium, and guide the lithium to be uniformly nucleated and deposited at the interface of the inner layer film/the negative electrode active material layer. In addition, the metal organic polymer has high mechanical strength, so that the formation of lithium dendrite is inhibited from the nucleation and growth stages, the generation of dead lithium is avoided, and the high safety of the battery and the reversible lithium ion intercalation/deintercalation and the deposition/stripping of metal lithium in the circulating process are ensured.
In any embodiment, the monolayer of the inner film is formed of an inner material selected from one or more of a zinc-based organic-inorganic composite film, an aluminum-based organic-inorganic composite film, and a titanium-based organic-inorganic composite film.
In any embodiment, the monolayer of the inner film comprises a simple metal.
In any embodiment, the inner film comprises 10 to 60 monolayers, such as 15 to 50 monolayers, 20 to 45 monolayers, or 25 to 35 monolayers.
Since the monolayer containing the simple metal has relatively high electron conductivity, if the thickness is too thick, lithium metal is deposited in the inner layer film, which may affect the structural stability of the inner/outer layer films.
In any embodiment, from 1 to 15, for example from 1 to 10 or from 2 to 6, of the monolayers in the inner film comprise the elemental metal.
In any embodiment, the elemental metal is selected from one or more of Zn, al, ti.
The metal simple substance M such as Zn, al, ti and the like can form M-Li alloy with metal lithium, and the nucleation overpotential of lithium is reduced.
In any embodiment, the monolayer of the outer layer film is formed from an organic polymer; optionally, the organic polymer is selected from one or more of polyurea, polyurethane, polyamide.
In any embodiment, the ratio of the number of monolayer layers of the outer layer film to the inner layer film is (2-5): 1.
in the present application, the outer layer film includes an organic polymer such as polyurea, has high electronic insulation, and inhibits internal deposition of metallic lithium in the inner layer/outer layer film. The inner layer film comprises a metal organic polymer, and the metal organic polymer optionally contains a part of metal simple substance, so that the inner layer film can have certain conductivity. To prevent the deposition of metallic lithium inside the inner film, the thickness of the inner film may optionally be reduced so that metallic lithium is deposited at the inner film/negative electrode active material layer interface. In addition, the inner layer film has a lithium-philic effect, and simultaneously has higher mechanical strength and rigidity compared with the outer layer film, and can effectively inhibit the growth of lithium dendrites.
The second aspect of the present application provides a method for preparing the negative electrode plate of the present application, comprising the following steps:
s1, preparing a negative electrode active material layer;
s2, covering the negative electrode active material layer on the inner layer film by a molecular layer deposition method in the step S1;
s3, covering the negative electrode active material layer covered on the inner layer film on an outer layer film by the molecular layer deposition method in the step S2,
wherein the negative electrode active material layer comprises graphite, the inner layer film comprises at least 10 monolayers of a metal organic compound, and the outer layer film comprises at least 40 monolayers of an organic polymer.
The molecular layer deposition is a preparation technology of an organic polymer and organic-inorganic hybrid film, can realize the deposition of a single molecular layer in each cycle, and has good process repeatability, film thickness, composition controllability and shape retention. The deposition principle is as follows: the thin film is produced by alternately introducing a plurality of reaction gases (or vapors) into the reactor in the form of gas pulses, chemisorbing and reacting by means of adsorbed molecules (such as hydroxyl or amino groups) remaining on the surface of the substrate. This allows the molecular layer deposition to have a self-limiting growth feature since each reactant participating in the reaction is confined to the molecule chemisorbed to the substrate surface.
In any embodiment, in the step S2, the process of depositing the monolayer of the inner film includes: placing the negative electrode active material layer described in step S1 as a substrate in a molecular layer deposition reaction chamber (S2-1); alternately pulsing a metal precursor gas (or vapor) and one or more organic precursor gases (or vapors) into the reaction chamber, and reacting the metal precursor gases (or vapors) and the substrate surface or a monolayer on the substrate surface by means of chemisorption to generate a monolayer (S2-2); optionally, a radical of a reducing agent is pulsed into the reaction chamber to reduce metal ions of the substrate surface (S2-3).
In any embodiment, in the step S3, the process of depositing the monolayer of the outer layer film includes: alternately pulsing one or more organic polymer precursor gases (or vapors) into the reaction chamber by using the negative electrode active material layer covering the inner layer film obtained in the step S2 as a substrate, and reacting the organic polymer precursor gases (or vapors) with the substrate surface or a monomolecular layer on the substrate surface by means of chemical adsorption to generate a monomolecular layer (S3); .
In any embodiment, in the step S2, the reduction reaction in the step (S2-3) may be placed before and/or after the pulsing of the organic precursor in the step (S2-2).
In any embodiment, the metal precursor is selected from one or more of diethyl zinc, trimethyl aluminum, titanium tetrachloride; or the organic precursor is selected from one or more of glycol, glycerol and hydroquinone; alternatively, the radical of the reducing agent is derived from at least one of hydrogen or ammonia.
In any embodiment, in the step S2, the reduction reaction in the step (S2-3) may be placed before and/or after the pulsing of the organic precursor in the step (S2-2).
In any embodiment, in step S3, the organic polymer precursor is selected from one or more of ethylene glycol, ethylenediamine, 1, 4-hydroquinone, glycerol, and hydroquinone.
The third aspect of the present application further provides a secondary battery, a battery module or an ion battery pack, wherein the secondary battery, the battery module or the battery pack includes the negative electrode plate of the present application.
The fourth aspect of the present application also provides an electric device, which includes at least one of the secondary battery, the battery module or the battery pack described in the present application, and the secondary battery, the battery module or the battery pack supplies electric energy to the electric device.
By covering the inner layer film and/or the outer layer film which are lithium-philic on the surface of the negative electrode active material layer, metal lithium is guided to be uniformly nucleated and deposited at the interface of the inner layer film/the negative electrode active material layer in the charging process of the battery, and the graphite/lithium metal composite negative electrode is formed in situ, so that the mixed working mode of reversible insertion/extraction of lithium ions and deposition/stripping of the metal lithium is realized, and the specific capacity of the negative electrode active material and the integral energy density of the battery are improved.
The negative pole piece can inhibit growth of lithium dendrites and relieve the unlimited volume effect of lithium metal. The inner layer film and/or the outer layer film covered on the surface of the negative active material layer has high mechanical strength and good flexibility, can relieve the volume effect of lithium metal while inhibiting the growth of lithium dendrites, maintains the stability of a negative pole piece structure, and improves the cycle life and the safety of the battery. Meanwhile, the negative active material layer is used as a carrier for lithium metal deposition, and the volume effect of the metal lithium layer on the surface of the negative pole piece is relieved to a certain extent.
Drawings
Fig. 1 depicts a schematic view of a negative electrode tab according to an embodiment of the present application.
Fig. 2 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 3 is an exploded view of the secondary battery according to the embodiment of the present application shown in fig. 2.
Fig. 4 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 5 is a schematic view of a battery pack according to an embodiment of the present application.
Fig. 6 is an exploded view of the battery pack according to the embodiment of the present application shown in fig. 5.
Fig. 7 is a schematic diagram of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Description of reference numerals:
1, a battery pack; 2, putting the box body on the box body; 3, discharging the box body; 4, a battery module; 5 a secondary battery; 51 a housing; 52 an electrode assembly; 53 a cap assembly; a current collector 01; a negative electrode active material layer 02; an inner layer film 03; the outer film 04.
Detailed Description
As disclosed herein, a "range" is defined in terms of lower and upper limits, with a given range being defined by the selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
In the present application, all embodiments and preferred embodiments mentioned herein may be combined with each other to form new solutions, if not specifically stated.
In the present application, all the technical features mentioned herein as well as preferred features may be combined with each other to form new technical solutions, if not specifically stated.
In the present application, all steps mentioned herein may be performed sequentially or randomly, if not specifically stated, but preferably sequentially. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
In the present application, the terms "include" and "comprise" as used herein mean open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that additional components not listed may also be included or included, or that only listed components may be included or included.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive and "one or more" mean "several" two or more.
In the description herein, the term "or" is inclusive, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, any one of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
In this context, percentages (%) or parts are percentages by weight or parts by weight relative to the composition, unless otherwise specified.
In this context, the sum of the contents of the individual components in the composition is 100%, if not stated to the contrary.
In this context, the sum of the parts of the components in the composition can be 100 parts by weight, if not stated to the contrary.
In this context, unless otherwise stated, "combinations thereof" means multi-component mixtures of the individual elements mentioned, for example two, three, four and up to the maximum possible multi-component mixtures.
The term "a" or "an" as used herein means "at least one" if not otherwise specified.
In this context, each reaction is carried out at normal temperature and pressure unless otherwise specified.
Negative pole piece
This application provides a negative pole piece in one aspect, the negative pole piece includes:
a negative electrode active material layer;
an inner layer film covering the negative electrode active material layer; and
an outer layer film covering the inner layer,
wherein the negative electrode active material layer comprises graphite, the inner layer film comprises at least 10 monolayers of a metal organic compound, and the outer layer film comprises at least 40 monolayers of an organic polymer.
In the present application, the anode active material layer may be a graphite anode active material layer commonly used in the field of lithium ion batteries. The anode active material layer is commercially available. In one embodiment, the negative electrode active material layer includes a negative electrode active material graphite, a conductive agent, a binder, a current collector, and/or the like. Optionally, the graphite is selected from one or more of natural graphite, artificial graphite and the like. In one embodiment, the negative electrode active material layer includes graphite and conductive carbon black. In another embodiment, the negative electrode active material layer includes graphite, conductive carbon black, and Styrene Butadiene Rubber (SBR). In another embodiment, the negative electrode active material layer includes graphite, conductive carbon black, styrene butadiene rubber, and carboxymethyl cellulose (CMC).
In the present application, the monolayer of the inner film is formed of one or more inner materials selected from Zincone (zinc-based organic-inorganic composite film), alucone (aluminum-based organic-inorganic composite film), titanicone (titanium-based organic-inorganic composite film), and the like. For example, the monolayer may be obtained by alternately pulsing a metal precursor, an organic precursor containing two or more functional groups (e.g., a diol (phenol), a polyol, a dicarboxylic acid, etc.), and optionally a reducing agent radical (e.g., a hydrogen radical, an ammonia radical, etc.) onto the substrate. The Zincone monomolecular layer can be obtained by the reaction of a zinc precursor (such as diethyl zinc), an organic precursor (such as ethylene glycol, hydroquinone and the like) and an optional reducing agent free radical (such as a hydrogen free radical) and the like; the Alucone monomolecular layer can be obtained by reacting an aluminum precursor (such as trimethylaluminum), an organic precursor (such as ethylene glycol, hydroquinone and the like) and an optional reducing agent free radical (such as a hydrogen free radical) and the like; the Titanicone monomolecular layer can be obtained by reacting a titanium precursor (such as titanium tetrachloride) with an organic precursor (such as ethylene glycol, glycerol and the like) and optionally a reducing agent radical (such as a hydrogen radical) and the like.
In the course of forming the monolayer, the monolayer may include a simple metal if a reducing agent radical (e.g., hydrogen radical) is used. Preferably, the monolayer is composed of a simple metal.
Preferably, the monolayer of the inner film comprises a Zincone monolayer.
The inner film may cover (e.g., completely cover) the surface of the anode active material layer, or may directly cover (e.g., completely cover) the surface of the anode active material layer.
The inner film comprises at least 10 monolayers, and optionally, the inner film comprises 10 to 60 monolayers. In one embodiment, the inner film comprises 15 to 50 monolayers, such as 20 to 45 monolayers and 25 to 35 monolayers.
In the monolayer of the inner layer film, optionally, a total of 1 to 15 monolayers include elemental metal, for example, 1 to 10 monolayers include elemental metal, or 2 to 6 monolayers include elemental metal. The monolayer including the simple metal may be randomly distributed in the monolayer of the inner film. For example, the monolayer including the simple metal substance is continuously distributed, or the monolayer including the simple metal substance is continuously distributed near the anode active material layer. Optionally, the monomolecular layer including the simple metal substance contacts a surface of the anode active material layer.
In one embodiment, the monomolecular layers containing the simple metal are all located at the bottom of the inner layer film (i.e., near the surface of the anode active material layer). And metal ions in the deposition layer close to the bottom in the inner layer film are reduced, so that lithium ions are captured in the charging process of the battery to form an M-Li alloy, and further, the uniform nucleation and deposition of lithium at the interface of the inner layer film/the negative electrode active material layer are promoted.
Optionally, the ratio of the monomolecular layer containing the elemental metal to the total number of the monomolecular layers in the inner layer film is 1: (6-16), for example, 1: (6-12). Since the monomolecular layer containing the simple metal has relatively high electron conductivity, if the monomolecular layer is too thick, lithium metal may be deposited in the inner layer film, which may affect the structural stability of the inner/outer layer films.
Alternatively, a metal simple substance M such as Zn, al, ti and the like can form an M-Li alloy with metal lithium, so that the nucleation overpotential of the lithium is reduced.
In the present application, the monolayer of the outer layer film is formed of an organic polymer. The organic polymer is selected from one or more of organic polymers such as polyurea, polyurethane, polyamide and the like. Optionally, the organic polymer is polyurea.
In the present application, the inner layer film/outer layer film covering the surface of the negative electrode active material layer has a double-layer structure with a uniform and controllable composition and structure, and is prepared by a molecular layer deposition method. The outer layer membrane is made of organic polymers such as polyurea with electronic insulation and good flexibility, so that side reactions between the negative active material layer and an electrolyte interface can be reduced, meanwhile, the volume change of the negative active material in the circulating process is relieved, the structural stability of the negative pole piece is maintained, and the circulating life of the battery is prolonged. The inner film is made of a high mechanical strength and lithium-philic metal organic compound such as Zincone. The metal organic compound contains lithium-philic metal sites such as zinc simple substance. The metal sites can preferentially react with lithium ions to generate M-Li alloy, reduce the nucleation overpotential of lithium, and guide lithium to be uniformly nucleated and deposited at the interface of the inner layer film/the negative electrode active material layer. In addition, the metal organic compound has high mechanical strength, so that the formation of lithium dendrite is jointly inhibited from the nucleation and growth stages, the separation of the lithium dendrite and a current collector is avoided to form dead lithium which loses electrochemical activity, the capacity attenuation of the battery is prevented, and the high safety of the battery and the reversible lithium ion intercalation/deintercalation and the deposition/exfoliation of metal lithium in the circulating process are ensured.
In one embodiment, the inner and outer films have a total thickness of between 1 and 100nm, optionally between 5 and 50 nm.
In one embodiment, the monolayer layer number ratio of the outer layer to the inner layer is (2-5): 1. the outer layer film described herein includes an organic polymer such as polyurea, has high electronic insulation, and inhibits deposition of metallic lithium inside the SEI outer layer. However, the inner layer film includes a metal organic compound, and the organic compound contains a part of simple metal, so that the inner layer film has certain conductivity. In order to prevent lithium from being deposited inside the inner film, it is optional to reduce the thickness of the inner film so that lithium is deposited at the inner film/negative electrode active material layer interface. However, considering that the inner layer film has higher mechanical strength and rigidity than the outer layer in addition to the lithium-philic effect, and can effectively suppress the growth of lithium dendrites, the inner layer film needs to have a certain thickness.
Preparation method of negative pole piece
Another aspect of the present application provides a method for preparing the negative electrode plate of the present application, including the following steps:
s1, preparing a negative electrode active material layer;
s2, covering the negative electrode active material layer on the inner layer film by a molecular layer deposition method in the step S1;
s3, covering the negative electrode active material layer covered on the inner layer film on an outer layer film by the molecular layer deposition method in the step S2,
wherein the negative electrode active material layer comprises graphite, the inner layer film comprises at least 10 monolayers of a metal organic compound, and the outer layer film comprises at least 40 monolayers of an organic polymer.
Alternatively, in the step S1, the method of preparing the anode active material layer may be: mixing and coating the negative active material graphite, a conductive agent and a binder on the surface of a current collector, and drying to form the negative active material layer.
Optionally, in the step S2, the process of depositing the monolayer of the inner film includes: placing the negative electrode active material layer described in step S1 as a substrate in a molecular layer deposition reaction chamber (S2-1); alternately pulsing a metal precursor gas (or vapor) and one or more organic precursor gases (or vapors) into the reaction chamber, and reacting the metal precursor gases (or vapors) and the substrate surface or a monolayer on the substrate surface by means of chemisorption to generate a monolayer (S2-2); optionally, a radical of a reducing agent is pulsed into the reaction chamber to reduce metal ions of the substrate surface (S2-3).
Optionally, in the step S3, the process of depositing the monolayer of the outer layer film includes: alternately pulsing one or more organic polymer precursor gases (or vapors) into the reaction chamber by using the negative electrode active material layer covering the inner layer film obtained in the step S2 as a substrate, and reacting the precursor gases with the substrate surface or a monomolecular layer on the substrate surface by means of chemical adsorption to generate a monomolecular layer (S3); .
Optionally, in the step S2, the metal precursor is selected from one or more of diethyl zinc, trimethyl aluminum and titanium tetrachloride.
Optionally, in the step S2, the organic precursor is selected from one or more of ethylene glycol, glycerol, and hydroquinone.
Optionally, in the step S2, the radical of the reducing agent is derived from at least one of hydrogen or ammonia. Alternatively, the radicals of the reducing agent may be generated by applying a voltage difference to a gas (e.g., at least one of hydrogen or ammonia) via an electrode.
Optionally, in the step S2, the sequence and number of pulses of the metal-containing precursor and the organic precursor in the step (S2-2) may be adjusted to achieve control of the composition and structure of the inner layer film.
Optionally, in the step S2, the controlling of the thickness of the inner film may be performed by controlling the number of times the metal-containing precursor and the organic precursor are pulsed in the step (S2-2), wherein the metal precursor or the organic precursor is considered to deposit one monolayer per pulse.
Alternatively, in the step S2, the reduction reaction in the step (S2-3) may be placed before and/or after the pulsing of the organic precursor in the step (S2-2).
Optionally, in the step S3, the organic polymer precursor is selected from one or more of ethylene glycol, ethylenediamine, 1, 4-hydroquinone, glycerol, and hydroquinone to form an organic polymer monolayer. The organic polymer includes but is not limited to one or more of polyurea, polyurethane, and polyamide.
Molecular Layer Deposition (MLD) principle: the molecular layer deposition is a preparation technology of an organic polymer and organic-inorganic hybrid film, can realize the deposition of a single molecular layer in each cycle, and has good process repeatability, film thickness, composition controllability and shape retention. The deposition principle is as follows: the thin film is produced by alternately introducing a plurality of reaction gases (or vapors) into the reactor in the form of gas pulses, chemisorbing and reacting by means of adsorbed molecules (such as hydroxyl or amino groups) remaining on the surface of the substrate. This allows the molecular layer deposition to have a self-limiting growth feature since each reactant participating in the reaction is confined to the molecule chemisorbed to the substrate surface.
The application also provides in one aspect a secondary battery, a battery module or a battery pack, the secondary battery, the battery module or the battery pack comprises the negative pole piece.
In yet another aspect, an electrical device is provided that includes at least one of a secondary battery, a battery module, or a battery pack as described herein, which provides electrical energy to the electrical device. The electric devices include, but are not limited to, mobile digital devices (e.g., mobile phones, notebook computers, etc.), electric vehicles (e.g., electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, and the like.
Fig. 1 depicts a schematic view of a negative electrode tab according to an embodiment of the present application. A negative pole piece capable of uniformly and controllably plating lithium is composed of a current collector 01, a negative active material layer 02, an inner layer film 03 and an outer layer film 04 which are distributed in sequence.
Fig. 2 is a schematic diagram of a secondary battery 5 according to an embodiment of the present application. Fig. 3 is an exploded view of the secondary battery according to the embodiment of the present application shown in fig. 2. The secondary battery 5 includes a case 51; an electrode assembly 52 and a cap assembly 53. Fig. 4 is a schematic view of the battery module 4 according to an embodiment of the present application. The battery module 4 includes a plurality of secondary batteries 5. Fig. 5 is a schematic diagram of the battery pack 1 according to the embodiment of the present application. Fig. 6 is an exploded view of the battery pack 1 according to the embodiment of the present application shown in fig. 5. The battery pack 1 includes a plurality of battery modules 4, an upper case 2, and a lower case 3. Fig. 7 is a schematic diagram of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Hereinafter, the effect of the negative electrode tab manufactured according to the embodiment of the present application on the performance of the electrochemical device is characterized based on the specific examples, but it should be particularly pointed out that the scope of protection of the present application is defined by the claims and is not limited to the above specific embodiments.
Examples
Example 1
Referring to fig. 1, a uniform and controllable lithium plating negative electrode plate is composed of a current collector 01, a negative electrode active material layer 02, an inner layer film 03 and a high-flexibility outer layer film 04 which are distributed in sequence. The preparation method comprises the following steps:
1. [ preparation of negative electrode active material layer ]
And (3) mixing the components in a mass ratio of 96:1:1.5:1.5 mixing the negative active material graphite, a conductive agent carbon black, a binder Styrene Butadiene Rubber (SBR), a thickener carboxymethyl cellulose (CMC) and solvent water to prepare slurry, coating the slurry on a copper foil, and drying the copper foil at 90 ℃ to obtain a negative active material layer.
2. [ inner layer film ]
(1) The negative electrode active material layer obtained in step 1 was placed as a substrate in a Molecular Layer Deposition (MLD) reaction chamber. (2) Diethyl zinc (DEZ) and Ethylene Glycol (EG) are respectively used as a metal precursor and an organic precursor, and the temperatures of the metal precursor and the organic precursor are respectively controlled at 25 ℃ and 85 ℃. The hydrogen radical is used as a reducing agent, the nitrogen is used as a carrier gas and a cleaning gas for conveying the precursor gas, the temperature of the reaction chamber is controlled at 135 ℃, and the vacuum degree is kept at 500mTorr. (3) the deposition process of the inner layer film comprises the following steps: the reaction precursor gas was alternately pulsed into the reaction chamber in the following time and sequence, (a) 0.05s/50s/0.05s/50s/0.5s/50s (DEZ pulse/purge/EG pulse/purge/reducing agent radical pulse/purge), the MLD process was cycled 5 times, (b) 0.05s/50s/0.05s/50s (DEZ pulse/purge/EG pulse/purge), the MLD process was cycled 10 times, and the negative active material layer covered with the inner layer film (30 molecular deposition layers) was obtained.
3. [ outer layer film ]
(1) Taking the negative electrode active material layer covering the inner layer film obtained in the step 2 as a substrate; (2) Ethylenediamine (ED) and 1, 4-p-Phenylene Diisocyanate (PDIC) are respectively used as two organic precursors, the temperatures of the two organic precursors are respectively controlled at 25 ℃ and 90 ℃, nitrogen is used as carrier gas and cleaning gas for conveying precursor gas, the temperature of a reaction chamber is controlled at 80 ℃, and the vacuum degree is kept at 800mTorr. (3) the deposition process of the outer layer film is as follows: 0.1s/50s/1s/50s (ED pulse/purging/PDIC pulse/purging), and the MLD process is cycled for 45 times to finally obtain the negative pole piece covering the inner 30 monolayer + the outer 90 monolayer, wherein 5 inner layers are deposition layers containing Zn elementary substance.
4. [ preparation of button cell ]
Mixing the negative pole piece obtained in the step 3, celgard 2400 diaphragm and NCM523 (LiNi) 0.5 Co 0.2 Mn 0.3 O 2 ) The positive electrode was assembled in order and 1mol/L LiPF was injected 6 (EC (ethylene carbonate): DMC (dimethyl carbonate) = DEC (diethyl carbonate) = 1: 1) electrolyte was prepared into a button cell in which the N/P ratio of graphite to the positive electrode of NCM523 was 0.82.
And standing the button cell for 12 hours at normal temperature, and then circulating for 3 circles at the rate of 0.1C/0.1C at the temperature of 25 ℃, further circulating for 300 circles at the rate of 0.2C/0.5C, wherein the charge-discharge window is 3.0V-4.3V. Finally, the cell surface capacity at 10 cycles at 0.2C/0.5C and the capacity retention rate of the cell after 300 cycles were measured.
Example 2
Basically the same as the step of the embodiment 1, the negative electrode sheet of the inner 60 monolayer + the outer 180 monolayer can be obtained by changing the MLD cycle number of the step (b) of the deposition process of the inner layer film in the step 2 to 25 and the MLD cycle number of the deposition process of the outer layer film in the step 3 to 90, wherein 5 monolayers containing a Zn simple substance are included in the inner layer.
Example 3
Basically the same as the step of the embodiment 1, the negative electrode sheet of the inner 90 monolayer + the outer 270 monolayer can be obtained by changing the MLD cycle number of the step (b) of the deposition process of the inner layer film in the step 2 to 40 and the MLD cycle number of the deposition process of the artificial SEI film outer layer in the step 3 to 135, wherein 5 monolayers containing a Zn simple substance are included in the inner layer.
Comparative example 1
Basically the same as the steps of the embodiment 1, the negative electrode sheet coated with the artificial SEI film (outer 120 molecular deposition layer) can be obtained by omitting the step 2 and changing the MLD cycle number of the deposition process of the outer layer film in the step 3 to 60.
Example 4
Basically the same as the step of the embodiment 1, the negative electrode sheet of the inner 70 monolayer layer + the outer 40 monolayer layer can be obtained by changing the MLD cycle number of the step (b) of the deposition process of the inner layer film in the step 2 to 35 and the MLD cycle number of the deposition process of the outer layer film in the step 3 to 20, wherein 5 deposition layers containing the Zn simple substance are provided in the inner layer.
Example 5
Basically the same as the step of the embodiment 1, the negative electrode sheet of 30 monolayers in the inner layer + 90 monolayers in the outer layer can be obtained only by changing the MLD cycle times of the steps (a) and (b) in the deposition process of the inner layer film in the step 2 to 10 and 5, respectively, wherein 10 monolayers in the inner layer are deposition layers containing Zn simple substance.
Example 6
Basically the same as the step of the embodiment 1, the negative electrode sheet of the inner 30 monolayers + the outer 90 monolayers of the deposition layer without the Zn simple substance can be obtained by omitting the step (a) of the deposition process of the inner layer film in the step 2 and changing the MLD cycle number of the step (b) to 15.
Comparative example 2
The difference from example 1 is that: steps 2 and 3 of coating the surface of the anode active material layer with the inner layer film and the outer layer film in example 1 are omitted.
[ Battery test calculation ]
1. Surface capacity of battery
Cell surface capacity = Cn positive electrode coating surface density positive electrode active material ratio, where Cn is the discharge gram capacity after n cycles.
2. Capacity retention ratio of battery
The battery capacity retention ratio Pn = Cn/C0 × 100%, where C0 is the initial reversible discharge capacity and Cn is the gram-of-discharge capacity after n cycles of cycles.
3. N/P ratio
N/P ratio = negative electrode capacity per unit area/positive electrode capacity = negative electrode active material gram capacity × negative electrode surface density × negative electrode active material ratio/(positive electrode active material gram capacity × positive electrode surface density × positive electrode active material ratio).
The test results are listed in table 1 below.
The comparative results for examples 1-3 show that: as the number of deposited layers increases, the surface capacity of the battery gradually decreases, and the cycle performance decreases. The comparison results of example 1 and comparative example 1 show that the inner film having lithium affinity and high mechanical strength is advantageous in promoting uniform deposition of metallic lithium at the inner film/negative electrode active material layer interface, inhibiting lithium dendrite formation, and thus improving the cycle stability of the battery. The comparison results of examples 1,4 and 5 show that the proportion of the inner layer film is too high or the proportion of the metal single layer in the inner layer film is too high, which can cause lithium metal to deposit on the inner layer film, destroy the structure of the inner layer film/outer layer film and influence the cycling stability of the battery.
The comparison result between the embodiment 1 and the embodiment 6 shows that the monomolecular layer containing the metal simple substance is helpful for realizing the uniform deposition of the lithium metal on the graphite surface, thereby better inhibiting the generation of lithium dendrites and improving the safety performance and the cycle performance of the battery. The comparison result of the embodiment 1 and the comparative example 2 shows that the inner layer film/the outer layer film on the surface of the negative active material layer is beneficial to inhibiting lithium dendrite and preventing the lithium dendrite and the current collector from separating to form dead lithium which loses electrochemical activity, and the cycle stability of the battery is improved.
Claims (17)
1. A negative electrode sheet, comprising:
a negative electrode active material layer;
an inner layer film covering the negative electrode active material layer; and
an outer film covering the inner film,
wherein the negative electrode active material layer comprises graphite, the inner layer film comprises at least 10 monolayers of a metal organic compound, and the outer layer film comprises at least 40 monolayers of an organic polymer.
2. The negative electrode sheet of claim 1, wherein the monolayer of the inner film is formed of an inner material selected from one or more of a zinc-based organic-inorganic composite film, an aluminum-based organic-inorganic composite film, and a titanium-based organic-inorganic composite film.
3. The negative electrode tab of claim 1 or 2, wherein the monolayer of the inner film comprises elemental metal.
4. A negative electrode sheet according to any one of claims 1 to 3, wherein the inner layer comprises 10 to 60 monolayers, such as 15 to 50 monolayers, 20 to 45 monolayers or 25 to 35 monolayers.
5. The negative electrode tab of any one of claims 1 to 4, wherein from 1 to 15, for example from 1 to 10 or from 2 to 6, of the monolayers of the inner film comprise the elemental metal.
6. The negative electrode plate as claimed in any one of claims 1 to 5, wherein the metal element is selected from one or more of Zn, al and Ti.
7. The negative electrode tab of any one of claims 1-6, wherein the monolayer of the outer layer film is formed from an organic polymer; optionally, the organic polymer is selected from one or more of polyurea, polyurethane, polyamide.
8. The negative electrode tab of any one of claims 1-7, wherein the ratio of the number of the monolayer layers of the outer layer film to the inner layer film is (2-5): 1.
9. a preparation method for preparing the negative pole piece of any one of claims 1 to 8 is characterized by comprising the following steps:
s1, preparing a negative electrode active material layer;
s2, covering the negative electrode active material layer on the inner layer film by a molecular layer deposition method in the step S1;
s3, covering the negative electrode active material layer covered on the inner layer film on an outer layer film by the molecular layer deposition method in the step S2,
wherein the negative electrode active material layer comprises graphite, the inner layer film comprises at least 10 monolayers of a metal organic compound, and the outer layer film comprises at least 40 monolayers of an organic polymer.
10. The method of claim 9, wherein in the step S2, the process of depositing the monolayer of the inner film comprises: placing the negative electrode active material layer described in step S1 as a substrate in a molecular layer deposition reaction chamber (S2-1); alternately pulsing a metal precursor gas (or vapor) and one or more organic precursor gases (or vapors) into the reaction chamber, and reacting the metal precursor gases (or vapors) and the substrate surface or a monolayer on the substrate surface by means of chemisorption to generate a monolayer (S2-2); optionally, radicals of a reducing agent are pulsed into the reaction chamber to reduce metal ions of the substrate surface (S2-3).
11. The method according to any one of claims 9 to 10, wherein in step S3, the process of depositing a monolayer of the outer layer film comprises: and (3) taking the negative electrode active material layer covering the inner layer film obtained in the step (S2) as a substrate, alternately pulsing one or more organic polymer precursor gases (or steam) to the reaction chamber, and enabling the organic polymer precursor gases to react with the substrate surface or a monomolecular layer on the substrate surface by means of chemical adsorption to generate a monomolecular layer (S3).
12. The method according to any of claims 10 to 11, wherein in step S2, the reduction reaction in step (S2-3) can be placed before and/or after the pulsing of the organic precursor in step (S2-2).
13. The method of any of claims 10-12, wherein the metal precursor is selected from one or more of diethyl zinc, trimethyl aluminum, titanium tetrachloride; or the organic precursor is selected from one or more of glycol, glycerol and hydroquinone; alternatively, the radical of the reducing agent is derived from at least one of hydrogen or ammonia.
14. The method according to any of claims 10 to 13, wherein in step S2, the reduction reaction in step (S2-3) can be placed before and/or after the pulsing of the organic precursor in step (S2-2).
15. The method of any one of claims 10 to 14, wherein in step S3, the organic polymer precursor is selected from one or more of ethylene glycol, ethylenediamine, 1, 4-hydroquinone, glycerol, and hydroquinone.
16. A secondary battery, a battery module or a battery pack, comprising the negative electrode sheet of any one of claims 1 to 8 or the negative electrode sheet prepared by the method of any one of claims 9 to 15.
17. An electric device comprising at least one of the secondary battery, the battery module, or the battery pack according to claim 16, which supplies electric power to the electric device.
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