CN115763705A - Silicon negative electrode and preparation method thereof, and all-solid-state lithium ion battery and preparation method thereof - Google Patents
Silicon negative electrode and preparation method thereof, and all-solid-state lithium ion battery and preparation method thereof Download PDFInfo
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Images
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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)
- Secondary Cells (AREA)
Abstract
The application provides a silicon cathode and a preparation method thereof, and an all-solid-state lithium ion battery and a preparation method thereof. The silicon negative electrode includes: a current collector; and the silicon active layer is formed on the surface of the current collector, the silicon active layer comprises a plurality of silicon lithium intercalation areas distributed in an island-shaped spaced mode and gaps positioned among the silicon lithium intercalation areas, the silicon lithium intercalation areas contain a silicon active material and a binder, the mass ratio of the silicon active material in the silicon lithium intercalation areas is 70-99.9 wt%, the silicon active material comprises any one or more of silicon, a silicon/carbon composite material, a silicon/titanium diboride composite material and a silicon/titanium nitride composite material, and the particle size of the silicon active material is 0.01-30 mu m. According to the silicon negative electrode disclosed by the embodiment of the invention, the silicon active layer with a porous structure is formed on the current collector, so that a containing space can be provided for silicon which expands in volume during lithium intercalation, the silicon active layer is prevented from cracking and falling during lithium deintercalation, and the cycle life of the all-solid-state lithium ion battery is prolonged.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a silicon cathode and a preparation method thereof, and an all-solid-state lithium ion battery and a preparation method thereof.
Background
With the development of science and technology, the traditional graphite negative electrode cannot meet the development requirement due to the limited theoretical specific capacity of the graphite negative electrode. Researchers have turned their attention to silicon anodes with theoretical specific capacities up to 4200mAh/g, which can significantly increase the energy density of batteries due to their high specific capacities, and moreover, silicon anodes are abundant in raw materials and environmentally friendly. However, the silicon negative electrode has a fatal disadvantage that the silicon expands more than 300% in volume when lithium is inserted, because in a liquid lithium ion battery, every time the electrolyte soaks one silicon negative electrode particle, a solid electrolyte interface film is formed on the surface of the silicon particle, and the expansion of the silicon during lithium insertion and lithium removal can cause continuous fracture and formation of the solid electrolyte interface phase on the surface of the silicon particle, so that active lithium is lost, and finally, the capacity of the silicon negative electrode is rapidly reduced.
Compared with a liquid lithium ion battery, the all-solid-state lithium ion battery adopts the solid electrolyte to replace the liquid electrolyte, so that only the solid electrolyte on the surface layer can be in contact with the surface layer of the negative electrode, the repeated generation of the interface phase of the solid electrolyte can be reduced, and the silicon negative electrode has great application potential in the all-solid-state lithium ion battery. At present, in order to relieve the expansion of silicon, most of the applications are based on the combination of nano silicon and a carbon skeleton, but the application is not applicable to an all-solid-state lithium ion battery because the carbon skeleton can not conduct lithium ions, the content of silicon in the silicon-carbon negative electrode is low, the high specific capacity of silicon can not be exerted, and the carbon skeleton can react with a solid electrolyte, so that the energy density of the all-solid-state battery is reduced, and the cycle life is shortened.
Disclosure of Invention
In view of the above, the present invention provides a silicon negative electrode capable of preventing a silicon active layer from cracking and falling off when lithium is deintercalated.
The invention also provides a preparation method of the silicon cathode.
The invention also provides an all-solid-state lithium ion battery.
The invention also provides a preparation method of the all-solid-state lithium ion battery.
According to a silicon anode of an embodiment of the first aspect of the present invention, the silicon anode includes:
a current collector; and
a silicon active layer formed on the surface of the current collector,
the silicon active layer comprises a plurality of silicon lithium intercalation areas distributed in an island-shaped spaced mode and gaps positioned among the silicon lithium intercalation areas, wherein the silicon lithium intercalation areas contain silicon active materials and a binder, the mass ratio of the silicon active materials in the silicon lithium intercalation areas is 70wt% -99.9wt%, the silicon active materials comprise any one or more of silicon, silicon/carbon composite materials, silicon/titanium diboride composite materials and silicon/titanium nitride composite materials, and the particle size of the silicon active materials is 0.01-30 mu m.
Furthermore, the silicon lithium intercalation areas are distributed in a checkerboard shape on the surface of the current collector.
Further, the area of the gap in the silicon active layer is 15 to 45%.
Further, the area ratio of the gap in the silicon active layer is 25 to 45%.
Further, the width of the gap is 10 μm to 1mm.
Further, the silicon active material has a particle size of 0.01 to 30 μm, and the binder is one or more selected from polyvinylidene fluoride (hereinafter, abbreviated as PVDF), polyacrylic acid (hereinafter, abbreviated as PAA), sodium carboxymethyl cellulose (hereinafter, abbreviated as CMC), nitrile rubber (hereinafter, abbreviated as NBR), styrene butadiene rubber (hereinafter, abbreviated as SBR), and styrene-butadiene-styrene block copolymer (hereinafter, abbreviated as SBS).
Further, the thickness of the silicon active layer is 20 μm or less.
The preparation method of the silicon negative electrode according to the embodiment of the second aspect of the invention comprises the following steps:
s1, providing a current collector;
s2, preparing negative electrode slurry, wherein the negative electrode slurry comprises a silicon active material, a binder and a solvent, the solid content of the negative electrode slurry is 40-70 wt%,
the silicon active material comprises any one or more of silicon, silicon/carbon composite material, silicon/titanium diboride composite material and silicon/titanium nitride composite material,
the particle size of the silicon active material is 0.01-30 μm;
s3, arranging the negative electrode slurry on the surface of the current collector to form a silicon active layer,
wherein the silicon active layer comprises a plurality of silicon lithium intercalation regions which are distributed in an island-shaped spaced manner and gaps positioned among the plurality of silicon lithium intercalation regions.
Further, the step S3 includes:
and printing the negative electrode slurry on the surface of the current collector by a screen printing method to form the silicon active layer.
Further, the step S3 includes:
and printing the negative electrode slurry on the surface of the current collector by a printing method to form the silicon active layer.
Further, the binder is selected from one or more of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethyl cellulose, nitrile rubber, styrene butadiene rubber and styrene-butadiene-styrene block copolymer.
The all-solid-state lithium ion battery according to the embodiment of the third aspect of the invention includes a silicon negative electrode, a solid electrolyte membrane, and a positive electrode, which are stacked in this order, wherein the silicon negative electrode is the silicon negative electrode described above.
The preparation method of the all-solid-state lithium ion battery according to the fourth aspect embodiment of the invention includes the steps of:
s100, providing a positive electrode;
s200, providing a sulfide electrolyte layer;
s300, preparing a silicon negative electrode according to the method of any embodiment of the first aspect of the invention;
s400, sequentially superposing the positive electrode, the sulfide electrolyte layer and the silicon negative electrode, and pressing to obtain a battery cell;
and S500, packaging based on the battery cell to obtain the all-solid-state lithium ion battery.
Further, the step S100 includes:
s110, providing a positive current collector;
s120, preparing positive electrode slurry;
s130, coating the positive electrode slurry on a positive electrode current collector, and heating and evaporating the solvent at 60-120 ℃ in a vacuum environment to obtain the positive electrode.
Further, in the step S120, the positive electrode slurry contains 60 to 100 parts by mass of a positive electrode active material coated with a coating material, 0 to 40 parts by mass of a sulfide electrolyte, 0 to 10 parts by mass of a conductive agent, and 0 to 10 parts by mass of a binder;
wherein the coating material is selected from Al 2 O 3 、SiO 2 、ZrO 2 、LiNbO 3 、Li 3 BO 3 、LiPO 3 、Li 2 ZrO 3 、Li 2 TiO 3 、TiO 2 And Ti 4 O 7 One or more of (a);
the chemical general formula of the anode active material is LiNi x Co y Mn z O 2 Wherein x is greater than or equal to 0.7, y is greater than or equal to 0, z is greater than or equal to 0, and x + y + z =1;
the sulfide electrolyte is selected from Li 6 PS 5 Cl、Li 6 PS 5 Cl 0.5 Br 0.5 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 10 GeP 2 S 12 、Li 7 P 3 S 11 、mLi 2 S·nP 2 S 5 、LiPON、Li 10 SnP 2 S 12 And LiS-SiS 2 And the mLi 2 S·nP 2 S 5 In the formula, m is more than or equal to 70 and less than or equal to 100, n is more than or equal to 0 and less than or equal to 30;
the conductive agent is selected from one or more of carbon fiber (hereinafter sometimes abbreviated as VCGF), carbon nanotube (hereinafter sometimes abbreviated as CNT), conductive carbon black (hereinafter sometimes abbreviated as SP) and graphene;
the binder is one or more selected from PVDF, PAA, CMC and SBR.
Further, the step S200 includes:
s210, mixing sulfide electrolyte, the binder and a solvent to obtain sulfide electrolyte slurry;
s220, coating the sulfide electrolyte slurry on a release film or a PET film, heating and evaporating the solvent at 40-100 ℃ in a vacuum environment, and removing the release film or the PET film to obtain the sulfide electrolyte layer.
Further, in the step S400, the battery cell is obtained by pressing for 3 to 10min under the pressure of 350 to 450 MPa.
The technical scheme of the invention has at least one of the following beneficial effects:
according to the silicon negative electrode provided by the embodiment of the invention, the silicon active layer is formed on the surface of the current collector, the silicon active layer comprises a plurality of silicon lithium embedding regions distributed in an island-shaped spaced manner and gaps positioned among the silicon lithium embedding regions, namely, the silicon active layer is formed into a porous structure, so that a containing space can be provided for silicon with volume expansion generated during lithium embedding, cracking and falling-off of the silicon active layer during lithium de-embedding are avoided, and the cycle life of the all-solid-state lithium ion battery is prolonged.
Drawings
FIG. 1 is a schematic structural diagram of a silicon negative electrode according to an embodiment of the present invention;
FIG. 2 is a flow chart of a method for manufacturing a silicon negative electrode according to an embodiment of the present invention;
fig. 3 is a flowchart of a method for manufacturing an all-solid-state lithium ion battery according to an embodiment of the present invention.
Reference numerals: 001. a current collector; 001a, a silicon lithium insertion region; 001b, a gap.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
Unless otherwise defined, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The use of "first," "second," and similar terms in the present application do not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. Also, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships are changed accordingly.
The silicon negative electrode according to the embodiment of the first aspect of the present invention will be described first in detail.
In order to provide sufficient accommodation space for silicon which expands in volume when lithium is intercalated, a porous structure is formed on the silicon negative electrode to buffer the lateral expansion of the silicon lithium intercalation layer. As shown in fig. 1, the silicon negative electrode includes: a current collector 001; and a silicon active layer formed on the surface of the current collector 001, wherein the silicon active layer comprises a plurality of silicon lithium intercalation regions 001a distributed in an island-shaped spaced manner and gaps 001b between the plurality of silicon lithium intercalation regions 001a. That is to say, a silicon active layer is formed on the surface of the current collector 001, and the silicon active layer comprises a plurality of silicon lithium intercalation regions 001a distributed in an island-shaped spaced manner and gaps 001b positioned among the silicon lithium intercalation regions 001a, so that the gaps 001b enable the silicon active layer to be formed into a porous structure, and further, a containing space can be provided for silicon with volume expansion generated during lithium intercalation, cracking and falling-off of the silicon active layer during lithium deintercalation are avoided, and the cycle life of the all-solid-state lithium ion battery is prolonged.
In some embodiments, the problem of deterioration of interface contact characteristics of the silicon active layer and the current collector 001 due to silicon expansion upon lithium intercalation may be improved by increasing the adhesion of the silicon active layer to the current collector 001. For this purpose, the silicon lithium insertion region 001a contains a binder in addition to the silicon active material, wherein the mass ratio of the silicon active material in the silicon lithium insertion region 001a is 70wt% to 99.9wt%. That is, by forming the silicon embedded lithium region 001a using a silicon active material and a binder, the silicon active material has a larger specific capacity than a carbon material, and the binder can improve the interface contact performance of the silicon embedded lithium region 001a with the current collector 001, further improving the cycle life of the all-solid-state battery. Further, the mass ratio of the silicon active material in the silicon lithium insertion region 001a may be, for example, 70wt%, 80wt%, or 99.9wt%, and compared with a dense silicon active layer, the silicon active layer of the present application may greatly increase the silicon content, so that the silicon negative electrode has a higher specific capacity, that is, by designing the components of the silicon active material and the binder, while obtaining a silicon negative electrode with a better specific capacity, the silicon active layer and the current collector 001 also have a good interface contact characteristic.
The silicon active material may be any one or more of silicon, silicon/carbon composite, silicon/titanium diboride composite, and silicon/titanium nitride composite, for example. Among them, in order to further increase the silicon content in the silicon negative electrode, silicon powder is preferably used.
The particle size of the silicon active material may be, for example, 0.01 μm to 30 μm. That is, the silicon active material may be, for example, a nanoscale powder, for example, having a particle diameter of 0.01 μm to 1 μm or less, or a micron-sized powder, for example, having a particle diameter of 1 μm to 30 μm, specifically, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm. The micron-sized silicon active material can keep better interface contact characteristic with the current collector 001, and compared with nano silicon, the micron-sized silicon active material can form larger interface clearance among large-sized silicon active materials to limit interface side reaction, so that the risk of cracking and falling of the silicon active layer during lithium intercalation and deintercalation can be further reduced, and the cycle life of the all-solid-state battery can be further prolonged.
Further, a plurality of silicon lithium intercalation areas 001a are distributed on the surface of the current collector 001 in a checkerboard shape. That is, as shown in fig. 1, the silicon lithium intercalation regions 001a and the gaps 001b are alternately arranged repeatedly, so that the gaps 001b are formed around the periphery of each silicon lithium intercalation region 001a, and a larger accommodating space can be provided for silicon which expands in volume during lithium intercalation, thereby preventing the silicon active layer from cracking and falling off, and further improving the cycle life of the all-solid-state lithium ion battery. It should be noted that the shape of the silicon lithium insertion region 001a is not limited to the square shape shown in fig. 1, and the silicon lithium insertion region 001a may also be one or more of a circle, a triangle, a polygon, and a special shape, for example. The fact that the silicon embedded lithium regions 001a are distributed on the surface of the current collector 001 in a checkerboard shape means that the current collector 001 is mostly in a square structure, and when the silicon embedded lithium regions 001a are square, the silicon embedded lithium regions 001a can be arranged on the current collector 001 as much as possible, so that the performance of the all-solid-state battery is improved. In addition, the method also has the advantages of convenient design and typesetting.
Further, the area ratio of the gap 001b in the silicon active layer is 15 to 45%. That is, the area ratio of the gap 001b in the silicon active layer may be, for example, 15%, 20%, 25%, 30%, 35%, 40%, 45%. Under the area ratio, on one hand, when the silicon expands due to lithium intercalation, the gap 001b can provide enough space to accommodate the expanded silicon, so that the cracking and falling of a silicon active layer can be avoided, and the cycle life of the all-solid-state lithium ion battery is further prolonged; on the other hand, more silicon lithium-embedded regions 001a can be formed on the silicon negative electrode, thereby ensuring better battery performance. If the area ratio of the gap 001b is greater than 45%, the gap 001b between any two adjacent silicon lithium-embedded regions 001a is enlarged, and the silicon lithium-embedded regions 001a formed on the limited current collector 001 are relatively reduced, so that the specific capacity of the silicon negative electrode is reduced, and the performance of the battery is influenced; if the area ratio of the gap 001b is less than 15%, the gap 001b between any two adjacent silicon lithium insertion regions 001a is smaller, and when the silicon expands in volume due to lithium insertion, the smaller gap 001b may not accommodate the silicon expanding in volume, so that the silicon active layer may crack and fall off when lithium is inserted, and the cycle life of the all-solid-state battery is reduced. Preferably, the area ratio of the gap 001b in the silicon active layer is 25 to 45%.
Further, the width of the gap 001b is 10 μm to 1mm. That is, the width of the gap 001b may be, for example, 10 μm, 20 μm, 50 μm, 100 μm, 300 μm, 500 μm, 700 μm, 900 μm, 1mm, based on the consideration of allowing the battery to have better battery performance and longer service life.
Further, the binder is one or more selected from PVDF, PAA, CMC, NBR, SBR and SBS. One or more of PVDF, PAA, CMC, NBR, SBR and SBS is/are selected as the binder, so that the interface contact performance and the battery performance of the silicon lithium-embedded region 001a and the current collector 001 can be further improved. Specifically, PVDF has high dielectric constant, good chemical stability and temperature characteristics, and has a positive effect of improving the adhesive force between the silicon active layer and the current collector 001; PAA can ensure the stability of the pole piece structure in the charging and discharging process of the battery, so that polar groups with high proportion are caused, and the PAA can form a film with the surface of a silicon active material through hydrogen bonds, and has excellent cycle performance; CMC is widely used as a binder of a water-based system negative electrode material, can obtain larger battery capacity, improve the cycle life of the battery and reduce the internal resistance of the battery; the NBR has a molecular chain structure containing cyano, oil resistance is superior to that of natural rubber, compared with other rubbers, the NBR has a wider use temperature, the long-term use temperature of the NBR is 120 ℃, meanwhile, the NBR has good low-temperature resistance, and the NBR has good chemical stability and good processability; the SBR binder has high binding strength, good mechanical stability and operability, is used as a binder in the battery industry, and has good effect and stable quality; SBS has good bonding strength, and has the characteristics of high solid matter content, quick drying and low temperature resistance.
In some embodiments, the interface contact characteristics of the silicon active layer and the current collector 001 may be further improved by controlling the thickness of the silicon active layer, which is 20 μm or less. That is, the thickness of the silicon active layer may be, for example, 19 μm, 15 μm, 10 μm, 5 μm, to further improve the interface contact characteristics of the silicon active layer and the current collector 001, and to help form the gap 001b by controlling the thickness of the silicon lithium intercalation layer.
The following describes a method for manufacturing a silicon negative electrode according to an embodiment of the present invention with reference to fig. 2, and the method for manufacturing a silicon negative electrode according to an embodiment of the second aspect of the present invention includes the following steps:
s1, providing a current collector 001;
s2, preparing negative electrode slurry;
s3, arranging the negative electrode slurry on the surface of the current collector 001 to form a silicon active layer,
wherein, the silicon active layer comprises a plurality of silicon lithium insertion regions 001a distributed in an island-shaped spaced manner and gaps 001b positioned between the plurality of silicon lithium insertion regions 001a.
That is, as shown in fig. 2, first, a current collector 001 is provided, then, a negative electrode slurry is prepared, and then, in step S3, the negative electrode slurry is disposed on the surface of the current collector 001 to form a silicon active layer having a plurality of silicon lithium insertion regions 001a and gaps 001b, and the plurality of silicon lithium insertion regions 001a are spaced apart in an island shape, and the gaps 001b are located between the plurality of silicon lithium insertion regions 001a, so that the gaps 001b on the silicon active layer allow the silicon active layer to be formed into a porous structure, which can provide a receiving space for silicon that expands in volume during lithium insertion, prevent the silicon active layer from cracking and falling off during lithium extraction, and improve the cycle life of the all-solid-state lithium ion battery.
The following describes each of the above S1 to S3 in detail.
First, step S1 of providing a current collector 001 is described.
The current collector 001 is at least one of a copper foil, a carbon-coated copper foil, a lithium magnesium alloy foil, a stainless steel foil and a lithium copper composite tape. That is, a copper foil, a carbon-coated copper foil, a lithium magnesium alloy foil, a stainless steel foil, and a lithium copper composite tape may be selected as the current collector 001 in consideration of the material properties and the cost.
Next, step S2, i.e., preparation of anode slurry, is explained.
In some embodiments, the negative electrode slurry includes a silicon active material, a binder, and a solvent, wherein a solid content of the negative electrode slurry is 40wt% to 70wt%. That is, 70 to 99.9 parts by mass of a silicon active material, 0.1 to 30 parts by mass of a binder, and a solvent are uniformly stirred to obtain a negative electrode slurry, and the solid content of the negative electrode slurry is made to be 40wt% to 70wt%. That is to say, by controlling the solid phase content in the cathode slurry within the above range, on one hand, the slurry has sufficient dispersibility and uniformity, and on the other hand, the silicon active layer obtained after the solvent is volatilized has higher mechanical strength, which is beneficial to improving the comprehensive performance of the all-solid-state battery.
The silicon active material and the binder are described above with reference to the silicon negative electrode, and detailed description thereof is omitted here. The solvent is not particularly limited as long as it can sufficiently disperse the silicon active material and the binder, and for example, an organic solvent such as methanol, ethanol, or acetone can be selected. Next, step S3, i.e., preparation of the silicon active layer, is explained.
In some embodiments, step S3 includes printing the anode paste on the surface of the current collector 001 by a screen printing method to form a silicon active layer. That is, a silicon active layer having a porous structure is formed on the current collector 001 by screen printing, and by selecting the shape and size of the mesh of the screen, silicon active layers having different patterns of silicon embedded lithium regions and different sizes of the gaps 001b can be formed on the current collector 001.
In some embodiments, step S3 includes printing the negative electrode paste on the surface of the current collector 001 by a printing method to form a silicon active layer. That is, a silicon active layer with a porous structure is formed on the current collector 001 by a printing method, the interface contact characteristic of the silicon active layer and the current collector 001 can be further improved by controlling the process parameters of the printing method, and a silicon lithium-embedded layer which is uniformly distributed is obtained, so that the comprehensive performance of the all-solid-state battery is further improved.
Here, it should be noted that the silicon anode of the first aspect example can be obtained according to the preparation method of the silicon anode of the second aspect example, and repeated descriptions thereof are omitted for the sake of brevity.
The all-solid-state lithium ion battery according to the third aspect of the invention includes a silicon negative electrode, a solid electrolyte membrane, and a positive electrode, which are stacked in this order, wherein the silicon negative electrode is the silicon negative electrode according to the first aspect of the invention. That is, the distribution and composition of the silicon lithium intercalation region 001a, the area ratio and width of the gap 001b, and the like in the silicon active layer described in the silicon negative electrode of the first embodiment can be applied to the all solid-state lithium ion battery of the third embodiment of the present invention, and the repeated description thereof is omitted for the sake of brevity.
A method for manufacturing an all-solid-state lithium ion battery according to an embodiment of the present invention is described below with reference to fig. 3, and the method for manufacturing an all-solid-state lithium ion battery according to the fourth aspect of the present invention includes the following steps:
s100, providing a positive electrode;
s200, providing a sulfide electrolyte layer;
s300, preparing the silicon negative electrode according to the preparation method of the silicon negative electrode in the embodiment of the second aspect;
s400, sequentially superposing the positive electrode, the sulfide electrolyte layer and the silicon negative electrode, and pressing to obtain a battery cell;
and S500, packaging based on the battery cell to obtain the all-solid-state lithium ion battery.
That is, in step S300, the components of the anode slurry and the method of forming the silicon active layer described in the method of manufacturing the silicon anode of the embodiment of the second aspect described above may be applied to the method of manufacturing the all-solid lithium ion battery of the embodiment of the fourth aspect of the present invention.
Next, the above steps S100, S200, and S400 will be described in detail.
First, step S100, i.e., the preparation of the positive electrode, is explained.
In some embodiments, step S100 comprises:
s110, providing a positive current collector;
s120, preparing positive electrode slurry;
and S130, coating the positive electrode slurry on a positive electrode current collector, and heating and evaporating the solvent at 60-120 ℃ in a vacuum environment to obtain the positive electrode.
Namely, the positive electrode slurry is coated on the positive electrode current collector, the positive electrode active layer is formed on the positive electrode current collector through high temperature, and the film is formed through high temperature heating, so that on one hand, the solvent can be quickly evaporated to dryness, and the production efficiency is improved; on the other hand, the interface contact characteristic of the positive active layer and the positive current collector can be improved, and the comprehensive performance of the all-solid-state lithium ion battery is further improved.
Further, in step S120, the positive electrode slurry contains 60 to 100 parts by mass of the positive electrode active material coated with the coating material, 0 to 40 parts by mass of the sulfide electrolyte, 0 to 10 parts by mass of the conductive agent, and 0 to 10 parts by mass of the binder. That is, the comprehensive performance of the all-solid-state lithium ion battery is further improved by adjusting and controlling the content of beneficial components in the positive electrode slurry.
The coating material is selected from Al 2 O 3 、SiO 2 、ZrO 2 、LiNbO 3 、Li 3 BO 3 、LiPO 3 、Li 2 ZrO 3 、Li 2 TiO 3 、TiO 2 And Ti 4 O 7 One or more of (a). That is, the coating of the positive active material with the coating material is based on the consideration of safety and battery performance, the coating material can prevent side reactions on the surface of the electrode, protect the substrate, reduce the heat generation of the battery, and select Al 2 O 3 、SiO 2 、ZrO 2 、LiNbO 3 、Li 3 BO 3 、LiPO 3 、Li 2 ZrO 3 、Li 2 TiO 3 、TiO 2 And Ti 4 O 7 One or more of the lithium ion batteries can be used as a coating material to effectively prevent side reaction on the surface of the electrode and further improve the comprehensive performance of the all-solid-state lithium ion battery.
The chemical general formula of the positive electrode active material is LiNi x Co y Mn z O 2 Wherein x is equal to or greater than 0.7, y is equal to or greater than 0, z is equal to or greater than 0, and x + y + z =1. That is, liNi x Co y Mn z O 2 Namely the nickel cobalt lithium manganate, has the advantages of high specific capacity and low cost and can provide large lithium manganateThe ability to flow current. In addition, the nickel cobalt lithium manganate has ideal crystal structure and small self-discharge, and can further improve the comprehensive performance of the all-solid-state lithium ion battery by being used as a positive active material.
Sulfide electrolyte is selected from Li 6 PS 5 Cl、Li 6 PS 5 Cl 0.5 Br 0.5 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 10 GeP 2 S 12 、Li 7 P 3 S 11 、mLi 2 S·nP 2 S 5 、LiPON、Li 10 SnP 2 S 12 And LiS-SiS 2 And one or more of (a), and mLi 2 S·nP 2 S 5 In the formula, m is more than or equal to 70 and less than or equal to 100, and n is more than or equal to 0 and less than or equal to 30. The sulfide electrolyte has high ion conductivity and high reaction activity, can improve the actual conductivity of lithium ions in the sulfide electrolyte, reduce the interface resistance of the positive electrode and the sulfide electrolyte layer, improve the interface stability and further improve the interface contact characteristic of the all-solid-state battery.
The conductive agent is one or more selected from VCGF, CNT, SP and graphene. That is, the conductive agent is one or more of VCGF, CNT, SP, and graphene, and the conductive agent can accelerate the transmission of ions and electrons, thereby improving the charge and discharge performance of the all-solid battery.
The binder is one or more selected from PVDF, PAA, CMC, NBR, SBR and SBS. That is, the binder is one or more of PVDF, PAA, CMC, NBR, SBR, and SBS, and the above binder may further improve the interfacial contact performance of the positive active layer and the positive current collector and the battery performance.
Next, step S200, i.e., preparation of the sulfide electrolyte layer, is explained.
In some embodiments, step S200 comprises:
s210, mixing sulfide electrolyte, a binder and a solvent to obtain sulfide electrolyte slurry;
s220, coating the sulfide electrolyte slurry on a release film or a PET film, heating and evaporating the solvent at 40-100 ℃ in a vacuum environment, and removing the release film or the PET film to obtain the sulfide electrolyte layer.
Namely, the slurry formed by mixing the sulfide electrolyte and the binder is used for forming the film, the binder can ensure the uniformity and the safety of the sulfide electrolyte slurry, the bonding effect among sulfide electrolyte particles is kept, and the comprehensive performance of the sulfide electrolyte layer is improved.
Next, step S400, i.e., the preparation of the battery cell, is explained.
In some embodiments, in step S400, the battery cell is obtained by pressing under a pressure of 350 to 450MPa for 3 to 10 min.
Namely, the positive electrode, the sulfide electrolyte layer and the silicon negative electrode are sequentially superposed, and the cell is obtained by optimizing and controlling the pressing process parameters of the cell, so that the comprehensive performance of the all-solid-state lithium ion battery is further improved.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
The present invention will be described in further detail below with reference to the preparation of the positive electrode, sulfide electrolyte layer and silicon negative electrode of the all-solid-state battery of specific examples.
Example 1
Preparation of positive electrode
And preparing the anode by adopting a wet process. Specifically, (1) first, 70 parts by mass of Al 2 O 3 Coated LiNi 0.8 Co 0.1 Mn 0.1 O 3 Ternary single crystal positive electrode material and 27 parts by mass of Li 6 PS 5 Firstly, uniformly mixing Cl sulfide electrolyte powder in a mixer or a mortar, then adding 1.5 parts by mass of a conductive agent VCGF, uniformly mixing in the mixer or the mortar again to obtain a mixture, dissolving 1.5 parts by mass of a binder SBS in a solvent anisole to form a binder solution, then adding the binder solution into the mixture, and continuously stirring uniformly to obtain anode slurry; (2) And uniformly transferring the positive slurry onto a positive current collector by a scraper coating method, and performing vacuum drying at 80 ℃ for 12h to obtain the positive electrode.
Preparation of sulfide electrolyte layer
And preparing the sulfide electrolyte layer by adopting a wet process. Specifically, (1) first in Li 6 PS 5 Adding a solvent into the Cl sulfide electrolyte powder, and uniformly mixing in a mixer or a mortar to form sulfide electrolyte slurry; (2) Coating the slurry on a centrifugal membrane in a scraper coating mode, drying for 12h at 60 ℃ in vacuum, and removing a release membrane or a PET (polyethylene terephthalate) membrane to obtain the sulfide electrolyte layer.
(III) preparation of negative electrode
And preparing the silicon cathode by a screen printing method. Specifically, (1) 80 parts by mass of a silicon active material, 20 parts by mass of a binder SBR, and a solvent are uniformly mixed to form a negative electrode slurry with a solid content of 60%, wherein the particle size of the silicon active material is 10 μm; (2) And forming a silicon active layer with the thickness of 10 mu m on the current collector by adopting a screen printing method, and drying for 12 hours in vacuum at the temperature of 80 ℃ to obtain the silicon cathode.
(IV) preparation of battery cell and all-solid-state lithium ion battery
The positive electrode, the sulfide electrolyte layer, and the silicon negative electrode were stacked in this order, and pressed under a pressure of 400MPa for 10min to obtain a cell of example 1.
In step S500, the cell of example 1 is packaged to obtain the all-solid-state lithium ion battery of example 1.
Comparative example
A cell was fabricated in the same manner as in example 1, except that the same negative electrode slurry was used to entirely cover the current collector to form a gapless silicon active layer having a thickness of 10 μm in the fabrication of the negative electrode.
The test results show that the capacity of the battery of example 1 can still reach 93% of the initial capacity after 100 cycles at 0.1C.
In contrast, the capacity retention of the battery of the comparative example was only 71% after 100 cycles at 0.1C.
From this, it is understood that the silicon negative electrode according to the present application greatly improves the cycle performance of the battery.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A silicon anode, comprising:
a current collector; and
a silicon active layer formed on the surface of the current collector,
the silicon active layer comprises a plurality of silicon lithium intercalation areas distributed in an island-shaped spaced mode and gaps positioned among the silicon lithium intercalation areas, wherein the silicon lithium intercalation areas contain silicon active materials and a binder, the mass ratio of the silicon active materials in the silicon lithium intercalation areas is 70wt% -99.9wt%, the silicon active materials comprise any one or more of silicon, silicon/carbon composite materials, silicon/titanium diboride composite materials and silicon/titanium nitride composite materials, and the particle size of the silicon active materials is 0.01-30 mu m.
2. The silicon negative electrode of claim 1, wherein a plurality of the silicon lithium intercalation regions are disposed in a tessellation on the surface of the current collector.
3. The silicon negative electrode according to claim 1, characterized in that the area proportion of the gap in the silicon active layer is 15 to 45%, preferably 25 to 45%.
4. The silicon anode of claim 1, wherein the gap has a width of 10 μm to 1mm.
5. The silicon anode of claim 1, wherein the binder is selected from one or more of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethylcellulose, nitrile rubber, styrene butadiene rubber, and styrene-butadiene-styrene block copolymer.
6. The silicon negative electrode as claimed in claim 1, wherein the thickness of the silicon active layer is 20 μm or less.
7. A method for producing a silicon negative electrode according to any one of claims 1 to 6, characterized by comprising the steps of:
s1, providing a current collector;
s2, preparing negative electrode slurry, wherein the negative electrode slurry comprises a silicon active material, a binder and a solvent, the solid content of the negative electrode slurry is 40-70 wt%,
the silicon active material comprises any one or more of silicon, silicon/carbon composite material, silicon/titanium diboride composite material and silicon/titanium nitride composite material,
the particle size of the silicon active material is 0.01-30 μm;
s3, arranging the negative electrode slurry on the surface of the current collector to form a silicon active layer,
wherein the silicon active layer comprises a plurality of silicon lithium intercalation regions which are distributed in an island-shaped spaced manner and gaps positioned among the plurality of silicon lithium intercalation regions.
8. The method according to claim 7, wherein the step S3 comprises:
printing the negative electrode slurry on the surface of the current collector by a screen printing method to form the silicon active layer; or,
and printing the negative electrode slurry on the surface of the current collector by a printing method to form the silicon active layer.
9. The method of claim 7, wherein the binder is selected from one or more of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethylcellulose, nitrile rubber, styrene butadiene rubber, and styrene-butadiene-styrene block copolymer.
10. An all-solid-state lithium ion battery comprising a silicon negative electrode, a solid electrolyte membrane, and a positive electrode laminated in this order, wherein the silicon negative electrode is the silicon negative electrode according to any one of claims 1 to 6.
11. A preparation method of an all-solid-state lithium ion battery is characterized by comprising the following steps:
s100, providing a positive electrode;
s200, providing a sulfide electrolyte layer;
s300, providing the silicon negative electrode of any one of claims 1 to 6;
s400, sequentially superposing the positive electrode, the sulfide electrolyte layer and the silicon negative electrode, and pressing to obtain a battery cell;
and S500, packaging based on the battery cell to obtain the all-solid-state lithium ion battery.
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