CN117060001A - Method for manufacturing separator of lithium ion storage battery - Google Patents

Method for manufacturing separator of lithium ion storage battery Download PDF

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Publication number
CN117060001A
CN117060001A CN202310273264.3A CN202310273264A CN117060001A CN 117060001 A CN117060001 A CN 117060001A CN 202310273264 A CN202310273264 A CN 202310273264A CN 117060001 A CN117060001 A CN 117060001A
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Prior art keywords
separator
particles
lithium ion
type
solid electrolyte
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Chinese (zh)
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M·昆泽
S·L·科赫
T·詹森
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Volkswagen AG
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Volkswagen AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides

Abstract

The application describes a method for producing a separator (26) for a lithium ion battery (20), comprising the following steps: providing (S10) a first type of particles (10) comprising a first oxide solid electrolyte material; providing (S11) a second type of particles (11) comprising a second oxide solid electrolyte material; mixing (S14) the first type particles (10) and the second type particles (11); and sintering (S16) a mixture comprising the first type of particles (10) and the second type of particles (11). It has now surprisingly been found that in particular a combination of oxide solid electrolyte materials results in a separator with good electrochemical properties.

Description

Method for manufacturing separator of lithium ion storage battery
Technical Field
The application relates to a method for manufacturing a separator of a lithium ion battery, comprising sintering different types of particles with different oxide solid electrolyte materials.
Background
Rechargeable electrochemical storage systems are becoming increasingly important in many areas of everyday life. High capacity energy storage devices, such as lithium ion batteries and capacitors, are used in a growing number of applications, including portable electronics, medical, transportation, grid-connected large energy storage, renewable energy storage, and Uninterruptible Power Supplies (UPS). For each of these applications, charge-discharge time and capacity of the energy storage device are decisive parameters. In addition, the size, weight, and/or cost of such energy storage devices are also important parameters. In addition, a lower internal resistance is also required for high power. The lower the resistance, the less the energy storage device is subject to limitations in outputting electrical energy. For example, in the case of a battery, internal resistance affects performance by reducing the total amount of useful energy stored by the battery and the ability of the battery to provide large currents. In addition, lithium ion batteries should be best able to achieve the desired capacity and cycle. However, current forms of lithium ion batteries often lack energy capacity and charge-discharge cycle times to meet these increasing applications.
As described above, lithium ion batteries are now widely used. For example, in consumer electronics, they are used in portable devices such as mobile phones, smartphones, notebook computers and tablet computers. In addition, lithium ion batteries are an important component of electric vehicles, since batteries are used for electric vehicles and hybrid vehicles, and thus become a component of mass production. Thus, in addition to the above performance requirements, ecological requirements are increasingly prominent. For example, the production of solid-state cells is very complex, and is characterized by a large number of precise assembly steps in the field of cell construction.
DE 10 201 8 217 507A1,DE 10 201 8 212 889A1 and EP 3 224 884 A1 describe solid electrolyte batteries.
However, the batteries known from the prior art are not entirely satisfactory.
The development of lithium metal batteries is considered the most promising technology to enable high energy density systems for energy storage. However, the current lithium metal secondary batteries have a problem of dendrite growth, making the lithium metal secondary batteries difficult to be practically used in portable electronic devices and electric automobiles. During several charge-discharge cycles microscopic lithium fibers, called dendrites, are formed on the lithium metal surface, which spread until they contact the other electrode. The current through these dendrites can short the battery. One of the most difficult aspects of manufacturing lithium metal secondary batteries is to develop a stable and efficient Solid Electrolyte Interface (SEI). Stable and efficient SEI provides an effective strategy for preventing dendrite growth, thus achieving improved cycling.
Thus, there remains a need for improved solid separators for lithium ion batteries having tailored properties.
Disclosure of Invention
According to the present application, the problem is solved by a method of manufacturing a lithium ion battery separator, comprising the steps of: providing a first type of particles comprising a first oxide solid electrolyte material; providing a second type of particles comprising a second oxide solid electrolyte material; mixing the first type of particles and the second type of particles; and sintering a mixture comprising the first type of particles and the second type of particles.
Different solid electrolytes have different properties. One of which has electrochemical stability to lithium and the other has higher particle conductivity. One electrolyte particle has plastic deformation capability, and the other electrolyte particle has better stability to ambient air. It has now surprisingly been found that especially a combination of a first type of particles comprising a first oxide solid electrolyte material and a second type of particles comprising a second oxide solid electrolyte material achieves a separator having particular advantages. This applies not only to the manufacturing process (which can be improved in this way), but also to the properties of the separator.
If two different oxide solid electrolyte materials are combined with each other, the product properties, in particular the conductivity of the grain boundary layer, and thus the mechanical and/or chemical stability, can be optimized in addition to the general processability, sintering temperature, process atmosphere, shape stability and intrinsic stress.
Special attention is paid to the sintering process in the context of the present application. During sintering, the material is manufactured or changed. The shape of the workpiece remains unchanged despite the heating, preferably under increased pressure, because the heating of the fine-grained ceramic or metallic material is preferably kept below the melting temperature.
However, a microscopic melting process can occur at least at the grain boundaries, which results in the formation of a mixed phase at the grain boundaries when two different solid electrolyte materials are used, as in the case of the present application, which contributes to particularly good electrochemical performance of the separator.
From a technical point of view, the necessary sintering temperature can be significantly reduced by sintering both oxide materials.
In addition, the mixed phase occurs at the melted grain boundaries of the two materials. These mixed phases may also be understood as part of a "solid solution". The properties of single-phase systems are mainly determined by the chemical composition, while the properties of multi-phase systems are affected by the phase distribution. The separator has higher mechanical and chemical stability due to the mixed phase and lower melting temperature than simple ceramics, thereby improving workability. These mixed phases also result in improved ionic conductivity, thereby improving the characteristics of the separator and thus the battery itself.
In the context of the present application, oxide solid material refers to any inorganic material containing oxygen as a component. Thus, an oxide having a predominantly pure ion-bonded fraction (for example in the case of lanthanum lithium zirconate or tantalate) is understood to be an oxide material. In addition, compounds such as lithium-aluminum-titanium-phosphoric acid are also considered to be included wherein oxygen forms part of the covalent bond, for example as part of the phosphate group.
However, at least at the grain boundaries, a melting process can take place, which results in the formation of a mixed phase when two different solid electrolyte materials are used, which, for example in the case of the application, contributes to particularly good electrochemical properties of the separator.
Special attention is paid to the sintering process in the context of the present application. Shrinkage typically occurs during this process as the particles of powdered raw material are compacted and the pores are compressed.
Basically, the sintering process is of great importance in ceramic production. In this case, it is necessary to distinguish between solid phase sintering and liquid phase sintering, in which melt also occurs, as has been disclosed in the context of mixed phase formation.
The relationship between the bonding area of the crystal grains and the particle diameter is important for properties such as strength and conductivity. For a given first oxide solid electrolyte and a given second oxide solid electrolyte, variables that can be adjusted and controlled are in particular temperature and initial grain size or grain size, since the evaporation pressure is temperature dependent.
The energy source for the solid process is the change in free energy between the neck and the surface of the particle. This energy produces mass transfer in the fastest way. If transfer occurs from the particle volume or grain boundaries between particles, particle reduction and pore destruction can occur. For many uniformly sized, higher porosity pores, pore shrinkage occurs faster when the boundary diffusion distance is smaller.
Controlling the temperature is of great importance for the sintering process, since grain boundary diffusion and volume diffusion depend on the temperature, the size and distribution of the material particles and the material composition.
According to a preferred embodiment of the method, a further temperature treatment is performed.
Thus, the sintered product attains its final properties such as strength, hardness or thermal conductivity. This can be controlled as required during sintering.
According to a preferred embodiment, the blank is formed in a preceding process step. Whereby the separator can obtain an accurate shape.
The method is described according to a preferred embodiment, wherein the first oxide solid electrolyte material comprises at least one lanthanum lithium zirconate and/or at least one lanthanum lithium tantalate.
The method is described according to a preferred embodiment, wherein the first oxide solid electrolyte material comprises, for example, garnet or lanthanum lithium zirconate Li 7 La 3 Zr 2 O 12 。
The method is described in accordance with a preferred embodiment wherein the second solid oxide electrolyte material comprises at least one material of the general formula Li 1 +xR x M 2-x (PO 4 ) 3 A NASICON-type or LISICON-type ceramic material represented, wherein M is selected from at least one element of the group of Ti, ge, zn, si and Hf; r is selected from at least one element of the group Al, B, sn, zr and Ge, and x is selected to be 0.ltoreq.x<3。
In this context, LISICON type or NASICON type refers to the structure of the solid electrolyte material.
NASICON stands for "sodium super ion conductor", commonly referred to as Na 1 +xZr 2 Si x P 3-x O 12 (wherein 0<x<3) Is a solid group of (2). More broadly, it is also used in similar compounds in which Na, zr and/or Si are substituted with equivalent elements. NASICON compounds have very high ionic conductivity, on the order of a magnitude comparable to the conductivity of liquid electrolytes. They are caused by Na ions jumping between interstitial sites of NASICON lattices.
The method is described according to a preferred embodiment wherein the second oxide solid electrolyte material comprises lithium aluminum titanium phosphate as a ceramic material of the NASICON type or LISICON type.
The method is described according to a particularly preferred embodiment, the first oxide solid electrolyte material comprising lanthanum lithium zirconate Li7La 3 Zr 2 O 12 (LLZO), and the second oxide solid electrolyte material includes Lithium Aluminum Titanium Phosphate (LATP). Both ion conductors are preferably lithium ion conductors. Garnet, perovskite and trans-perovskite are also contemplated.
According to a particularly preferred embodiment, the first oxide solid electrolyte material comprises lanthanum lithium zirconate Li7La 3 Zr 2 O 12 LLZO. The second oxide solid electrolyte material comprises lithium aluminum titanium phosphate, LATP, wherein the two solid electrolyte materials are present at 80% relative to the total weight of the composition: 20 to 20:80 weight percent, preferably 70:30 to 30:70 weight percent.
LLZO is stable, particularly to lithium metal, and has very high grain conductivity. However, LLZO has a very high sintering temperature.
LATP also has good grain conductivity, but grain boundary conductivity is low. Unlike grain conductivity, grain boundary conductivity does not describe conductivity inside the grain, but rather conductivity across the grain boundary.
If the two electrolytes are combined together, the product properties, in particular the conductivity and mechanical/chemical stability of the grain boundary layer, can be optimized in addition to sintering temperature, process atmosphere, shape stability and intrinsic stress.
The method is described in accordance with a preferred embodiment, the method further comprising: at least one coating layer is formed on a separator formed as a substrate.
According to a further preferred embodiment, the method is described, the coating being formed after sintering.
Such additional coatings may be used to further improve the performance of the separator. This embodiment is described as being particularly preferred, since this does not lead to an adverse structural change of the separator.
According to a preferred embodiment, a method of manufacturing a separator for a lithium ion battery is described, wherein the coating is formed as a cathode side coating on a substrate.
According to a preferred embodiment, a method of manufacturing a separator for a lithium ion battery is described, wherein the coating is formed as an anode side coating on a substrate.
According to a preferred embodiment, the layer structure described on the separator is used to form a gradient.
Thus, the first solid electrolyte and the second solid electrolyte may be uniformly distributed in the separator film or have a distribution gradient. The formation of the gradient according to the present embodiment will be exemplified below. The number may be modified and adapted by those skilled in the art as required for the particular situation. In this case, the first and second solid electrolytes are preferably mixed at 50: 50. The preferred anode-oriented side of the solid electrolyte separator consists essentially of 100% of the first solid electrolyte, while the cathode-oriented side of the separator consists of 100% of the second solid electrolyte. By applying different solid electrolyte mixtures layer by layer, a gradient is achieved through the solid electrolyte separator. For example, a first layer consisting of only the first solid electrolyte is established. Onto which a second layer is applied, for example from a mixture of a first and a second solid electrolyte at 75: 25. In the next step, the mixing ratio of the first and second solid electrolytes is 50: an optional third layer of 50 composition is applied. Next, a mixture ratio of 25 of the first and second solid electrolytes was applied during the coating process: 75, and an optional fourth layer. In the example given, the termination is constituted by a layer consisting of only the second solid electrolyte.
Lithium ion batteries or lithium ion batteries within the meaning of the present application are rechargeable batteries containing lithium. Lithium ions migrate from the negative electrode to the positive electrode through the electrolyte during discharge and back to the negative electrode during charge. For example, lithium ion batteries use intercalation lithium compounds on the positive electrode.
Although conventional batteries known from the prior art generally have graphite on the negative electrode, according to the application the negative electrode comprises, and preferably consists of at least 80% by weight, preferably at least 90% by weight, and preferably essentially of metallic lithium.
According to a particularly preferred embodiment, the battery has an electrode comprising or consisting of metallic lithium as negative electrode, wherein the separator comprises LLZO as oxide solid electrolyte material. LLZO is particularly suitable for use in combination with metallic lithium electrodes because LLZO is stable with respect to lithium.
The battery according to the present application uses a solid electrolyte in the separator layer.
Thus, in addition to the efficiency improvement of the production technology, performance is improved.
The separator acts as a barrier to electrically isolate the two electrodes from each other to avoid internal shorting. Meanwhile, the separator must be permeable to ions so that the electrochemical reaction can be performed in the battery. The separator should be thin so that the internal resistance is as low as possible and a high packing density can be obtained.
In addition to the first oxide solid electrolyte material and the second oxide solid electrolyte material, other solid electrolyte materials may be included.
Such other materials that are optionally used in addition to the first solid oxide electrolyte that is necessarily present and the second solid oxide electrolyte that is necessarily present are:
sulfide Li 2 S-P 2 S 5 ,Li 2 S-SiS 2 And Li (lithium) 2 S-GeS 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or
Oxide Li 7 La 3 Zr 2 O 12 (LLZO) and Li 3x La 2/3-3x TiO 3 (LLTO); and/or
Spodumene Li 6 PS 5 X (x=cl, br and I), li 7 PS 6 und Li 7 PSe 6 。
Furthermore, the following additional materials may also be used:
β-Li 3 PS 4 、Li 10 SiP 2 S 12 、Li 10 GeP 2 S 12 (with LiH for Li) 2 PO 4 Coating (original text: liH) 2 PO 4 Beschichtung zu Li))、77.5Li 2 S–22.5P 2 S 5 、LiI-Li 2 S–P 2 S 5 、80Li 2 S–20P 2 S 5 、Li 6 PS 5 Cl、Li 6.6 P 0.4 Ge 0.6 S 5 I、Li 3 PS 4 Glass, 70Li 2 S-29P 2 S 5 –1P 2 O 5 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 PEO-LiTFSI and Al-Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 Composite material, PBA-LiClO 4 And Li (lithium) 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Composite material, PEO-LiTFSI and/or SI-PEO-LiTFSI.
According to another embodiment, the separator material comprises only an oxide solid electrolyte.
According to a preferred embodiment, the battery has a current collector. The current collector is understood to be a structure within the electrode of the battery, which is designed such that current can flow between the pole of the battery and the active material of the battery.
The current collector is an element connecting the lithium ion battery and an external circuit, and has a great influence on the capacity, performance and long-term stability of the lithium ion battery. Conventional current collectors, al and Cu films have been used from the first commercial lithium ion battery, and the thickness of these current collectors has been reduced over the past twenty years to increase energy density.
The positive electrode may preferably include a lithium-based positive electroactive material that can perform lithium intercalation and deintercalation, alloying and dealloying, or plating and stripping while acting as a positive connector.
Different inorganic lithium compounds are considered as cathode materials. For example:
NMC (NCM) -lithium nickel cobalt manganese oxide (LiNiCoMnO 2 )；
LFP-lithium iron phosphate (LiFePO) 4 /C)；
LNMO-lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 O 4 )；
NCA-lithium nickel cobalt aluminum oxide (LiNiCoAlO) 2 )；
Lithium LMO-manganese oxide (LiMn) 2 O 4 ) Or (b)
LCO-cobalt oxide lithium (LiCoO) 2 )。
Specifically, according to this alternative embodiment, the negative electrode may comprise lithium metal and/or a lithium alloy. In other variations, the negative electrode may comprise a silicon-based negative electroactive material, such as a silicon alloy, silicon oxide, or a combination thereof, and may be further mixed with graphite in certain instances.
According to the embodiments described below, the secondary battery may have a layered structure. The use of a solid electrolyte achieves an advantageous layer structure. In such embodiments, the solid electrolyte is also referred to as a separator layer.
Further, a lithium ion battery is described according to a preferred embodiment, wherein the thickness of the separator layer is 0.1 to 25 μm.
Furthermore, according to a preferred embodiment, a lithium ion battery is described that further comprises a cathode stack.
Furthermore, according to a preferred embodiment, a lithium ion battery is described, further comprising a cathode stack with separator layers.
The described stacking solution provides an overall flexible system, in particular by using a flexible solid electrolyte layer or separator layer. This is flexible due to its structure and manufacturing process. The core of the hybrid collector (or hybrid collector) may compensate for mechanical stresses. This makes it possible to produce a cylindrical solid-state battery. Another advantage is that no additional sintering process is required during production.
Further solutions may be found in the dependent claims and combinations thereof.
The different embodiments of the application mentioned in the present application may be advantageously combined with each other, unless stated otherwise in individual cases.
Drawings
The application is described in the following embodiments with reference to the related drawings. In the drawings:
fig. 1 shows a lithium ion battery assembly with electrodes;
fig. 2 illustrates a method of manufacturing a separator according to an embodiment of the present application;
FIG. 3a shows a sintering process for a homogeneous mixture of particles;
FIG. 3b illustrates a sintering process comprising a mixture of a first type of particles and a second type of particles;
FIG. 4 shows a grain boundary comprising a mixture of a first type of particle and a second type of particle;
FIG. 5 shows a separator with additional coating according to an embodiment, an
Fig. 6 shows a separator with an additional coating according to another embodiment.
Detailed Description
Fig. 1 shows a lithium ion battery 20 with electrodes 22, 24. Positive electrode 24 and negative electrode 22 are formed ofThe separator 26 separates. Separator 26 is capable of conducting lithium ions between negative electrode 22 and positive electrode 24. The separator is solid. However, in conventional lithium ion batteries, the electrolyte is a nonaqueous liquid electrolyte solution containing a lithium salt dissolved in an organic solvent or a mixture of organic solvents. Unlike such conventional solutions, the present application relates to a secondary battery having a solid electrolyte. Different inorganic lithium compounds are considered as positive electrode materials. For example, lithium nickel cobalt manganese oxide (LiNiCoMnO 2 ) Lithium nickel manganese spinel (lini0.5mn1.5o4) or lithium nickel cobalt aluminum oxide ((LiNiCoAlO) 2 ). Further, lithium manganese oxide (LiMn 2 O 4 ) Or cobalt oxide lithium (LiCoO) 2 ) And is also a suitable material. Graphite is generally used as the anode material, but lithium metal is preferably used in the present application.
Fig. 2 illustrates a method of manufacturing a separator 26 according to an embodiment of the present application. The method for manufacturing separator 26 of a lithium ion battery according to the flow chart first includes providing S10 a first type of particles including a first oxide solid electrolyte material. Further, a second type of particles including a second oxide solid electrolyte material are added and these particles are mixed with each other S14. After this, sintering S16 of the mixture including the first type particles 10 and the second type particles 11 is performed, thereby finally obtaining the separator 26.
The first oxide solid electrolyte material comprises lanthanum lithium zirconate Li 7 La 3 Zr 2 O 12 LLZO. The second oxide solid electrolyte material includes lithium aluminum titanium phosphate, LATP. Both solid electrolyte materials were in the order of 50:50 is added and sintered. But other numbers may be used. Such a combination has proven to be particularly preferred compared to other combinations of solid electrolyte materials (e.g., combinations of LLZO with perovskite or LATP with perovskite). However, perovskite or inverse perovskite are also possible. Garnet is also possible.
Fig. 3a shows a sintering process S16 of a homogeneous mixture of particles. The homogeneous powder is first formed into the shape of the workpiece S16.1 to be manufactured. Shaping and optionally subsequent drying in the production of ceramics. In order to adhere the powder particles together, binders may also be used if desired. The blank or body obtained by pressing is compacted below the melting temperature by a subsequent heat treatment S16.2 and then further heated to maintain the temperature S16.3. This is also a decisive distinction from pure melts, since the raw materials do not melt completely. Sintering is therefore also assigned to the type of manufacturing process of forming, however, where the material properties can also be "changed", and is therefore preferably controlled by process control. The sintered product is then cooled S16.4.
Fig. 3b shows a sintering process S16 for a particle mixture comprising a first type of particles 10 and a second type of particles 11, as is the case in the present application.
After mixing the first particles 10 and the second particles 11, the powder mass is formed into the shape of the workpiece S16.1 to be manufactured. The billets are formed by shaping or pressing the mixed starting materials under high pressure in a mold. This already corresponds to the desired shape of the sintered product.
In this case, the blank or blank is compacted below the melting temperature S16.2 by a subsequent heat treatment. If an adhesive is used, it is preferable to eliminate the adhesive at a temperature of 300 to 800 ℃. According to step 16.3, the actual sintering is carried out at a temperature above 700 ℃, preferably between 900 ℃ and 1200 ℃.
This is the actual sintering according to the application, where the powder particles are amplified and fused during the high temperature treatment of the green body. The open porosity of the sintered part is significantly reduced. Until now, the desired component properties, such as strength, hardness and in particular electrical conductivity, have not been produced. Unlike the melt, the raw materials do not completely melt.
The sintered composition includes a first particle and a second particle, having a large internal surface area and thus a large surface energy. Each system strives to reach a state of lowest free enthalpy, which is available upon sintering. The surface energy decreases as individual particles become larger.
This is especially true in systems with mixed oxide particles, as is the case with the present application. This is because a microscopic melting process occurs at the grain boundaries, which results in the formation of a mixed phase at the grain boundaries when two different solid electrolyte materials are used, as in the case of the present application, which contributes to particularly good electrochemical performance of the separator. From a technological point of view, by sintering two oxide materials, the necessary sintering temperature can be significantly reduced. The sintered product S16.4 is then cooled.
Fig. 4 shows a grain boundary comprising a mixture of first type particles 10 and second type particles 11. The figure shows grain boundaries 14 between particles of the same type and grain boundaries 15 between particles of different types.
During sintering, the grain boundaries partially merge. This preferably occurs due to the collision properties of the mixture of the first solid electrolyte material and the second solid electrolyte material at the grain boundaries 15. Thus, a mixed phase is formed at the grain boundaries 15 that are fused together, which can also be understood as a partial "solid solution". The properties of single-phase systems are mainly determined by the chemical composition, while the properties of multi-phase systems are affected by the phase distribution. The separator has higher mechanical and chemical stability due to the mixed phase and lower melting temperature than simple ceramics, thereby improving workability. These mixed phases formed at the grain boundaries 15 further result in improved ionic conductivity, thereby improving the characteristics of the separator 26, and thus the characteristics of the battery itself.
Fig. 5 shows a separator 26 according to an embodiment of the application. As described above, the separator 26 is obtained by providing the sintered substrate 100. The substrate is obtained by sintering the first particles 10 and the second particles 11 and has corresponding advantageous properties. The embodiments described herein further design the separator 26 described previously by forming further layers over the separator 26. The separator 26 according to the present embodiment further has first layers 112, 122 of the first and second coatings 110, 120 on one or both sides of the substrate 100, respectively. The first coating 110 is preferably disposed on the cathode side and the second coating 120 is preferably disposed on the anode side within the battery. The coating applied to the cathode side is preferably a sulfide coating. According to a preferred embodiment, the layer structure described on the separator is used to form (by varying the respective amount ratios in the substrate and layer) a gradient associated with the distribution of the amounts of the first solid oxide electrolyte and the second solid oxide electrolyte.
Fig. 6 shows a separator 26 according to another embodiment of the application. The separator 26 is obtained by providing a substrate 100. The next step is to apply a first composition on both sides of the substrate 100 to form the first layers 112, 122 of the first and second coatings 110, 120, respectively. Then, in a further step, a second composition forming a second layer 114, 124 is applied to the first layers 112, 122 of the first and second coatings 110, 120. The first coating 110 is in turn preferably disposed on the cathode side within the battery, while the second coating 120 is preferably disposed on the anode side. According to a preferred embodiment, the additional layer structure described on the separator serves to further distinguish the gradient already described in fig. 5 with respect to the mass distribution of the first solid oxide electrolyte and the second solid oxide electrolyte. Thus, different quantitative ratios may be formed in the additional layers 114, 124 than in the first layers 112, 122 and/or the substrate 100, and thus, gradients may be formed more differently.
List of reference numerals
S10 providing particles of the first type
S11 providing a second type of particles
S14 mixing of the first type particles and the second type particles
S16 sintering
S16.1 shaping
S16.2 compaction
S16.3 heating
S16.4 Cooling
10. Particles of the first type
11. Particles of the second kind
14 grain boundaries between particles of the same type
15 grain boundaries between different types of particles
20. Storage battery
22. Negative electrode
24. Positive electrode
26. Partition board
100. Separator substrate
110. First cathode side coating of separator
112. First layer of separator
114. Second layer of separator
120. Second coating of separator anode side
122. First layer of separator
124. A second layer of separator.

Claims (15)

1. A method for manufacturing a separator (26) for a lithium ion battery (20), comprising the steps of:
-providing (S10) particles (10) of a first type comprising a first oxide solid electrolyte material;
-providing (S11) a second type of particles (11) comprising a second oxide solid electrolyte material;
-mixing (S14) the first type of particles (10) and the second type of particles (11); and
-sintering (S16) a mixture comprising particles of a first type (10) and particles of a second type (11).
2. The method according to claim 1, characterized in that the first oxide solid electrolyte material comprises at least one lanthanum lithium zirconate and/or at least one first oxide having a garnet structure.
3. The method of claim 2, wherein the first oxide solid electrolyte material comprises lanthanum lithium zirconate Li 7 La 3 Zr 2 O 12 。
4. The method of any of the preceding claims, wherein the second oxide solid electrolyte material comprises at least one metal represented by the general formula Li 1 +xR x M 2-x (PO 4 ) 3 A NASICON-type or LISICON-type ceramic material represented, wherein M is selected from at least one element of the group of Ti, ge, zn, si and Hf; r is selected from at least one element of the group Al, B, sn, zr and Ge, and x is selected to be 0.ltoreq.x<3。
5. The method of claim 4, wherein the second oxide solid electrolyte material comprises lithium aluminum titanium phosphate.
6. The method of claim 5, wherein the method further comprises:
raising the temperature to 300-800 ℃ for the first time; and
the temperature is further increased to between 900 ℃ and 1200 ℃.
7. Method for manufacturing a separator (26) for a lithium ion battery (20) according to one of the preceding claims, characterized in that it further comprises:
-forming at least one coating (110, 120) for forming a gradient on a separator (26) designed as a substrate (100).
8. The method for manufacturing the separator (26) of the lithium ion battery (20) of claim 7, wherein a gradient with respect to the amount distribution of the first solid oxide electrolyte material and the second solid oxide material is formed with the coating (110, 120).
9. The method for manufacturing a separator (26) for a lithium ion battery (20) according to claim 8, wherein said coating is formed as a cathode side coating (110) on a substrate (100).
10. The method for manufacturing a separator (26) for a lithium ion battery (20) according to claim 9, wherein said coating is formed as an anode side coating (120) on a substrate (100).
11. Separator (26) for a lithium ion battery (20), obtained by the method according to any of the preceding claims.
12. A method of manufacturing a lithium ion battery (20), the method comprising:
-providing a separator (26) according to the method of any one of claims 1 to 9;
-providing an anode (22) comprising metallic lithium;
-providing a cathode (24).
13. A lithium ion battery (20) obtained by the method according to claim 12.
14. The lithium ion battery (20) of claim 13, wherein the lithium ion battery (20) is formed as a stacked battery.
15. Use of a lithium ion battery (20) according to claim 13 or 14 in a motor vehicle.
CN202310273264.3A 2022-05-12 2023-03-20 Method for manufacturing separator of lithium ion storage battery Pending CN117060001A (en)

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DE102022204655.2A DE102022204655A1 (en) 2022-05-12 2022-05-12 Method for producing a separator for a lithium-ion battery

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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10593998B2 (en) 2014-11-26 2020-03-17 Corning Incorporated Phosphate-garnet solid electrolyte structure
US10840513B2 (en) 2018-03-05 2020-11-17 Samsung Electronics Co., Ltd. Solid electrolyte for a negative electrode of a secondary battery and methods for the manufacture of an electrochemical cell
DE102018212889A1 (en) 2018-08-02 2020-02-06 Robert Bosch Gmbh Composite materials conducting lithium ions and their production and their use in electrochemical cells
DE102018217507A1 (en) 2018-09-20 2020-03-26 Robert Bosch Gmbh Composite material and its use in an electrochemical solid-state cell
DE102019135702A1 (en) 2019-12-23 2021-06-24 Schott Ag Solid-state lithium ion conductor materials, solid-state ion conductor material powders and methods for their manufacture
US20210257656A1 (en) 2020-02-14 2021-08-19 GM Global Technology Operations LLC Lithium phosphate coating for lithium lanthanum zirconium oxide solid-state electrolyte powders

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