Patent Publication Number: US-2022238922-A1

Title: All-solid battery

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application claims priority to Japanese Patent Application No. 2020-190815 filed on Nov. 17, 2020, incorporated herein by reference in its entirety. 
     TECHNICAL FIELD 
     The present disclosure relates to an all-solid battery. 
     BACKGROUND ART 
     An all-solid battery is a battery that has a solid electrolyte layer between a cathode and an anode and has an advantage that simplification of a safety device can be easily devised as compared with a liquid-based battery having an electrolytic solution containing a flammable organic solvent. 
     Patent Document 1 discloses that a Si-based active material is made to be porous, volume expansion rate is reduced, and the lifespan of a battery is improved. 
     Patent Document 2 discloses that the Si-based active material is a secondary particle having a plurality of primary particles, and when the volume of the secondary particle is V P  and the void volume of the secondary particle is V V , the ratio of V V  to V P  (V V /V P ) is 0.3 or more and 0.6 or less.
     Patent Document 1: JP2018-120866A   Patent Document 2: JP2020-087882A   

     Since the Si-based active material greatly varies in volume during charging and discharging, electrical resistance easily increases due to cracking and the like by repeating the charging and discharging cycle. Even in the prior art, the electrical resistance after the cycle being large is a problem. This disclosure has been made in consideration of the above-described actual condition, and a main object of which is to provide the all-solid battery that can reduce the electrical resistance after the cycle. 
     SUMMARY 
     To solve the above-described problem, this application discloses an all-solid battery that includes a cathode layer, an anode layer, and a solid electrolyte layer. The solid electrolyte layer is formed between the cathode layer and the anode layer. The anode layer contains a Si-based active material. The Si-based active material is a secondary particle having a plurality of primary particles. When a sum of void volume inside the primary particles included in the secondary particle is set to V V1  and a sum of void volume between the primary particles included in the secondary particle is set to V V2 , a ratio of the V V1  to the V V2  calculated by V V1 /V V2  is 0.8 or more and 5 or less. 
     The all-solid battery this application discloses can reduce the resistance after the cycle. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic cross-sectional view of an all-solid battery  10 . 
         FIG. 2  is a view schematically illustrating one secondary particle  20 . 
         FIG. 3  is a graph representing the result of working examples and comparative examples. 
     
    
    
     DESCRIPTION OF EMBODIMENTS 
     The following describes an all-solid battery of this disclosure in detail. 
       FIG. 1  is a schematic cross-sectional view illustrating one example of the all-solid battery in this disclosure. Further,  FIG. 2  is an image view of the cross section of one certain Si-based active material  20  (secondary particle  20 ) in this disclosure. The all-solid battery  10  illustrated in  FIG. 1  has a cathode layer  12 , an anode layer  11 , and a solid electrolyte layer  13  arranged between the cathode layer  12  and the anode layer  11 . Furthermore, the all-solid battery  10  has a cathode current collector  15  that collects current of the cathode layer  12  and an anode current collector  14  that collects current of the anode layer  11 . The following describes each configuration. 
     1. Anode Layer 
     The anode layer  11  is a layer containing at least an anode active material. 
     The anode layer  11  contains the Si-based active material  20  as the anode active material. The Si-based active material  20  is an active material that can be alloyed with Li. Examples of the Si-based active material  20  include a Si simple substance, a Si alloy, and a Si oxide. The Si alloy contains a Si element as a main component. The proportion of the Si element in the Si alloy may be, for example, 50 mol % or more, may be 70 mol % or more, or may be 90 mol % or more. 
     Examples of the Si oxide include SiO 2 . 
     The Si-based active material  20  is the secondary particle  20  having a plurality of primary particles  21  as illustrated in  FIG. 2 . 
     Here, for the Si-based active material  20 , when a sum of void volume inside the primary particles  21  included in the secondary particle  20  is set to V V1  and a sum of the void volume between the primary particles  21  included in the secondary particle  20  is set to V V2 , the ratio of V V1  to V V2  calculated by V V1 /V V2  is 0.8 or more and 5 or less. This can lower the initial electrical resistance while maintaining (or improving) suppressing effect of expansion and contraction of the Si-based active material  20 . This is considered to be because the area of a contact interface between the Si particle and the solid electrolyte expands and a solid diffusion distance inside the Si decreases. This can reduce the electrical resistance value after a cycle. V V1 /V V2  is 1 or more, or 1.5 or more. Further, V V1 /V V2  is 5 or less, or 3 or less. 
     When V V1 /V V2  becomes large, pores appear even on the surface of the primary particles  21 , a specific surface area becomes large, and a reactive area increases, which is considered to reduce the electrical resistance. Furthermore, since a true specific gravity of the primary particles  21  becomes small, the number of particles increases and the reactive area increases as long as the design has the same capacity, which is considered to reduce the electrical resistance. Further, the voids in the primary particles  21  can absorb the expansion of the primary particles  21  themselves to some extent, and even if the ratio of V V2  becomes small by that amount, it is considered that the expansion as the secondary particle  20  can be controlled. However, when V V1 /V V2  exceeds 5, the true specific gravity of the primary particles  21  becomes small, and thus, with the design having the same capacity, the number of particles increases, a film thickness becomes too thick. Accordingly, the electrical resistance in the thickness direction increases, the region which absorbs the expansion as the secondary particle  20  becomes small, cycle deterioration is likely to occur, and the resistance after the cycle increases. On the other hand, when V V1 /V V2  is smaller than 0.8, the reactive area becomes relatively small, and the initial electrical resistance increases, leading to the increase in the resistance after the cycle. 
     V V1  and V V2  can be obtained, for example, as follows. 
     That is, the secondary particle  20  includes roughly divided 3 volume voids of V V1 , V V2 , and other V α , and the respective volume can be obtained by isolating these in the following way. 
     (1) All the void volume included in the secondary particle  20  is obtained by the gas absorption. This is V V1 +V V2 +V α . 
     (2) The secondary particle  20  is crashed to the primary particle level and the void volume is obtained by gas absorption. Since this represents V V1 , this is defined as V V1 . 
     (3) Therefore, V V2 +V α , can be also obtained from (1) and (2). 
     (4) An area which belongs to V V2  and an area which belongs to V α , are obtained by SEM image processing of the cross section of the secondary particle  20 . This is regarded as the volume ratio of V V2  and V α , and from this, V V2  is obtained. 
     Further, in this disclosure, when a long side length of the primary particle  21  is set to a, a short side length is set to b, and the ratio of b to a is set to b/a, the value of b/a is, for example, 0.5 or more, may be 0.6 or more, or may be 0.8 or more. On the other hand, the value of b/a may be 1, or may be less than 1. When this kind of primary particle  21  is used, an all-solid battery having more satisfactory cycle characteristics can be obtained. 
     The long side length a and the short side length b can be obtained by measuring the cross-sectional image of the primary particles  21 . Specifically, one primary particle  21  is specified from the cross-sectional image, a straight line is drawn in a specified region, and the longest portion in the length is defined as the long side a. On the other hand, the portion which is perpendicular to the long side a and the shortest in the length is defined as the short side b. From these values, b/a is obtained. This operation is also performed on other primary particles  21  to obtain an average value of b/a. The number of samples is large, is, for example, 20 or more, may be 50 or more, or may be 100 or more. 
     Although an average grain diameter (D 50 ) of the primary particles  21  is not specifically limited, the average grain diameter (D 50 ) is, for example, 50 nm or more, or may be 100 nm or more. On the other hand, the average grain diameter (D 50 ) of the primary particles is, for example, 1 μm or less, or may be 500 nm or less. 
     The Si-based active material  20  in this embodiment may contain a needle-shaped conductive material between the plurality of primary particles  21 . Here, the needle shape means an elongated shape in which the length of the long side is twice or more the length of the short side. Further, the needle shape may be a linear shape or a curved shape and can be said as a rod shape or a fibrous shape. Further, a plurality of needle-shaped conductive materials may be tangled to be present. Such a conductive material plays a role of a filler by existing between the plurality of primary particles  21  and is estimated to impose a positive effect on maintaining framework of the Si-based active material  20  when the Si-based active material  20  expands and contracts. 
     Although the conductive material is not particularly limited as long as it is needle-shaped, examples include VGCF (gas phase method carbon fiber), CNT (carbon nanotube), and the like. 
     In the needle-shaped conductive material, the length of the long side is twice or more the length of the short side, and for example, may be 10 times or more, or may be 50 times or more. On the other hand, the length of the long side may be 500 times or less the length of the short side or may be 100 times or less. 
     The long side of the needle-shaped conductive material is, for example, 5 μm or more and 15 μm or less. Further, the short side of the needle-shaped conductive material is, for example, 50 nm or more and 200 nm or less. 
     The Si-based active material  20  may contain a conductive material having other shape than the needle shape, such as a granular shape. Examples of the granular-shaped conductive material include acetylene black (AB), Ketjen black (KB), and the like. 
     When the needle-shaped conductive material is contained in the Si-based active material  20 , a proportion is not specifically limited. However, for example, the proportion is 0.5 weight % or more, and may be 1 weight % or more. Further, the proportion of the conductive material is, for example, 10 weight % or less, or may be 5 weight % or less. If the proportion of the conductive material is too small, the effect of including the conductive material may not be sufficiently enjoyed. On the other hand, if the proportion of the conductive material is too large, productivity may get worse. 
     In the Si-based active material  20 , a binder may exist between the adjacent primary particles  21 . Examples of the binder include polyimide. Further, a common binder used for the anode layer may be used. The proportion of the binder included in the Si-based active material  20  is, for example, 0.5 weight % or more, and may be 1 weight % or more. On the other hand, the proportion of the binder included in the Si-based active material is, for example, 5 weight % or less. 
     The Si-based active material  20  can be produced, for example, as follows. 
     For the primary particles  21 , for example, by mixing Li and Si in a mortar to prepare LiSi alloy and treating this LiSi alloy with ethanol, the primary particles  21  which are porous (have the voids constituting V V1 ) can be obtained. 
     A slurry containing the obtained primary particles  21 , a conductive material (also referred to as a first conductive material), a binder, and a dispersion medium is prepared. Here, examples of the binder include a high strength binder, such as polyimide (for example, 1 weight % or more and 5 weight % or less with respect to Si), and examples of the dispersion medium include water. Further, examples of a method of forming the slurry include a method of kneading a mixture containing the primary particles  21 , the first conductive material, the binder, and the dispersion medium using a kneading device, such as a planetary mixer. A solid content concentration of the slurry is, for example, 5 weight % or more and 30 weight % or less. 
     Next, the obtained slurry is processed by granulation to turn to secondary particles. Examples of the granulation processing include a process using a nozzle type spray dryer. The amount of solution sending is, for example, 20 mL/h or more and 200 mL/h or less. The spray gas pressure is, for example, 0.1 MPa or more and 0.4 MPa or less. Further, the drying temperature is, for example, 140° C. or more and 200° C. or less. Further, for example, when the slurry contains a polyimide precursor as the binder, heat treatment is performed after the granulation process to form the polyimide. The heat treatment temperature is, for example, 250° C. or more and 350° C. or less. The heat treatment period is, for example, 1 hour or more and 10 hours or less. The heat treatment atmosphere is an inert atmosphere or a vacuum. This is because oxidation of the Si-based active material can be prevented. 
     The void (void constituting V V2 ) of the Si-based active material  20  (secondary particle  20 ) can be adjusted by appropriately setting manufacturing conditions. For example, when the solid content of the slurry reduces, the void tends to increase. On the other hand, for example, when the binder amount increases, the void tends to decrease. 
     The anode layer  11  may contain only the Si-based active material  20  as the anode active material or may contain other active materials. In the latter case, the proportion of the Si-based active material in all the anode active materials may be 50 weight % or more, may be 70 weight % or more, or may be 90 weight % or more. 
     The proportion of the anode active material in the anode layer  11  is, for example, 20 weight % or more, may be 30 weight % or more, or may be 40 weight % or more. On the other hand, the proportion of the anode active material in the anode layer is 95 weight % or less, may be 90 weight % or less, or may be 80 weight % or less. 
     Further, the anode layer  11  may contain at least one of the solid electrolyte and the binder, as necessary. Examples of the above-described solid electrolyte include inorganic solid electrolytes, such as a sulfide solid electrolyte, an oxide solid electrolyte, a nitride solid electrolyte, and a halide solid electrolyte. Examples of the sulfide solid electrolyte include an Li element, an X element (X is at least one kind of P, Si, Ge, Sn, B, Al, Ga, and In), and a solid electrolyte containing an S element. Further, the sulfide solid electrolyte may further contain at least one of an O element and a halogen element. Further, examples of the oxide solid electrolyte include the Li element, a Y element (Y is at least one kind of Nb, B, Al, Si, P, Ti, Zr, Mo, W, and S), and the solid electrolyte containing the O element. Further, examples of the nitride solid electrolyte include Li 3 N, and examples of the halide solid electrolyte include LiCl, LiI, and LiBr. Examples of the above-described binder include rubber-based binders, such as butylene rubber (BR) and styrene butadiene rubber (SBR), and fluoride-based binders, such as polyvinylidene fluoride (PVDF). 
     Further, the anode layer  11  may contain a second conductive material other than the conductive material (first conductive material) contained in the Si-based active material  20 . Examples of the second conductive material include a carbon material. Examples of the carbon material include particle-shaped carbon materials, such as acetylene black and Ketjen black, and fibrous-shaped carbon materials, such as a carbon fiber, a carbon nanotube, and a carbon nanofiber. The second conductive material may be different from or may be the same as the first conductive material. 
     When the anode layer  11  contains the first conductive material and the second conductive material, the proportion of the first conductive material in all the conductive materials inside the anode layer may be 50 weight % or more, may be 70 weight % or more, or may be 90 weight % or more. 
     The thickness of the anode layer  11  is, for example, 0.1 μm or more and 1000 μm or less. Examples of a method of forming the anode layer include a method of applying and drying the above-described slurry which contains at least the Si-based active material and the dispersion medium and has turned to the secondary particles. Note that it is only necessary to add the second conductive material when preparing the above-described slurry. 
     2. Cathode Layer 
     The cathode layer  12  is a layer containing at least a cathode active material. Further, the cathode layer  12  may contain at least one of the solid electrolyte, the conductive material, and the binder, as necessary. 
     Examples of the cathode active material include an oxide active material. Examples of the oxide active material include rock salt layer type active materials, such as LiCoO 2 , LiMnO 2 , LiNiO 2 , LiVO 2 , and LiNi 1/3 Co 1/3 Mn 1/3 O 2 , spinel type active materials, such as LiMn 2 O 4  and Li (Ni 0.5 Mn 1.5 )O 4 , and olivine type active materials, such as LiFePO 4 , LiMnPO 4 , LiNiPO 4 , and LiCoPO 4 . Further, on a surface of the cathode active material, a coat layer containing an Li ionic conductive oxide may be formed. This is because a reaction between the cathode active material and the solid electrolyte can be suppressed. 
     Examples of a shape of the cathode active material include a particle shape. Although an average secondary particle (D 50 ) of the cathode active material is not specifically limited, the average secondary particle (D 50 ) is, for example, 10 nm or more, or may be 100 nm or more. On the other hand, the average secondary particle diameter (D 50 ) of the cathode active material is, for example, 50 μm or less, or may be 20 μm or less. 
     The proportion of the cathode active material in the cathode layer  12  is, for example, 20 weight % or more, may be 30 weight % or more, or may be 40 weight % or more. On the other hand, the proportion of the cathode active material is, for example, 80 weight % or less, may be 70 weight % or less, or may be 60 weight % or less. 
     For the solid electrolyte and the binder used in the cathode layer  12 , since the explanation is the same as the content described in the anode layer  11  above, the description thereof is omitted here. 
     Examples of the conductive material include a carbon material. Examples of the carbon material include particle-shaped carbon materials, such as acetylene black and Ketjen black, and fibrous-shaped carbon materials, such as a carbon fiber, a carbon nanotube, and a carbon nanofiber. 
     The thickness of the cathode layer  12  is, for example, 0.1 μm or more and 1000 μm or less. Examples of a method of forming the cathode layer include a method of applying and drying a slurry containing at least the cathode active material and a dispersion medium. 
     3. Solid Electrolyte Layer 
     The solid electrolyte layer  13  is a layer arranged between the cathode layer and the anode layer. The solid electrolyte layer  13  contains at least a solid electrolyte and may contain a binder, as necessary. For the solid electrolyte and the binder, since the explanation is the same as the anode layer  11  above, the description thereof is omitted here. Above all, the solid electrolyte layer contains the sulfide solid electrolyte as the solid electrolyte. 
     The thickness of the solid electrolyte layer  13  is, for example, 0.1 μm or more and 1000 μm or less. Examples of a method of forming the solid electrolyte layer  13  include a method of compression molding of the solid electrolyte. 
     4. Other Members 
     The all-solid battery  10  in this embodiment has at least the anode layer  11 , the cathode layer  12 , and the solid electrolyte layer  13  as described above. Furthermore, usually, the all-solid battery  10  has the cathode current collector  15  that collects current of the cathode layer  12  and the anode current collector  14  that collects current of the anode layer  11 . Examples of a material of the cathode current collector  15  include stainless steel, aluminum, nickel, iron, titanium, and carbon. On the other hand, examples of a material of the anode current collector  14  include stainless steel, copper, nickel, and carbon. Note that the thicknesses and shapes of the cathode current collector  15  and the anode current collector  14  are selected appropriately according to an application of the battery. Further, the all-solid battery  10  may have a battery case  16  which houses the anode layer  11 , the cathode layer  12 , and the solid electrolyte layer  13  as described above. 
     5. All-Solid Battery 
     In some embodiments, the all-solid battery in this disclosure is an all-solid lithium battery. Further, although the all-solid battery in this disclosure may be a primary battery or may be a secondary battery as the secondary battery can be charged and discharged repeatedly and is useful as, for example, an on-vehicle battery. Further, the all-solid battery in this disclosure may be a single battery or may be a laminated battery. The laminated battery may be a monopolar type laminated battery (parallel connection type laminated battery) or may be a bipolar type laminated battery (series connection type laminated battery). Examples of the shape of the all-solid battery include a coin type, a laminated type, a cylindrical type, and a square type. 
     Note that the aspect of this disclosure is not limited to the above embodiment. The above embodiment is only illustrative. The technical scope of this disclosure encompasses any technology as long as the technology has substantially the same configuration as those of the technical ideas recited in the appended claims of this disclosure and provides similar operational advantages. 
     Working Example 
     [Preparation of a Cathode Structure] 
     A cathode active material (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) and a sulfide solid electrolyte (Li 2 S—P 2 S 5 ) were weighed so that the volume ratio of the cathode active material to the sulfide solid electrolyte became 75 to 25. Further, a PVDF binder was weighed to be 1.5 weight parts with respect to 100 weight parts of the cathode active material, and a conductive auxiliary agent (VGCF, manufactured by Showa Denko) was weighed to be 3.0 weight parts with respect to 100 mass parts of the cathode active material. These materials were mixed and adjusted so that the solid content became 63 weight %. Afterwards, these materials were kneaded for 1 minute using an ultrasonic sound wave homogenizer to obtain a cathode composition in a slurry state. The obtained cathode composition was applied on the surface of a cathode current collector (aluminum foil, manufactured by Showa Denko), and underwent the process of drying by heating to form a cathode. The cathode was roll-pressed at 25° C. and at a linear pressure of 1 ton/cm to obtain a cathode structure having the cathode current collector and a cathode layer. 
     [Preparation of an Anode Active Material] 
     Li and Si were mixed in a mortar to prepare a LiSi alloy and this LiSi alloy was treated with ethanol to obtain porous primary particles. 
     The prepared primary particles, a conductive material having a length of 6 μm and a diameter of 150 nm (VGCF, manufactured by Showa Denko), a polyimide precursor (polyamic acid), and water were mixed and kneaded with a planetary mixer to obtain a slurry. The obtained slurry was dried using a nozzle type spray dryer to turn to secondary particles. Afterwards, the slurry underwent heat treatment under an inert atmosphere to obtain an Si-based active material. 
     For the obtained Si-based active material, V V1 /V V2  was obtained. Table 1 shows V V1 /V V2  in Working example 1 to Working example 5, Comparative example 1, and Comparative example 2. Adjustment of V V1 /V V2  in each Working example were conducted by adjusting V V1  by the mixing ratio of Li and Si and the ethanol treatment speed, and by adjusting V V2  by the spray pressure and the drying speed of the spray dryer. 
     [Preparation of an Anode Structure] 
     The prepared Si-based active material and the sulfide solid electrolyte (Li 2 S—P 255 ) were weighed so that the volume ratio of the anode active material to the sulfide solid electrolyte became 60 to 40. Further, the PVDF binder was weighed to be 1.5 weight parts with respect to 100 weight parts of the Si-based active material, and the conductive auxiliary agent (VGCF) was weighed to be 3.0 weight parts with respect to 100 weight parts of the Si-based active material. These materials were mixed and adjusted so that the solid content became 45 weight %. Afterwards, these materials were kneaded for 1 minute using the ultrasonic sound wave homogenizer to obtain an anode composition in a slurry state. The obtained anode composition was applied on the surface of an anode current collector (nickel foil) using an applicator and dried by heating. Afterwards, it was roll-pressed at 25° C. and at a linear pressure of 1 ton/cm to obtain an anode structure having the anode current collector and an anode layer. Although V V1 /V V2  shown in Table 1 is a measurement result before pressing, it has been confirmed by the inventor that V V1 /V V2  hardly varies before and after pressing. 
     [Preparation of a Battery] 
     The sulfide solid electrolyte (Li 2 S—P 2 S 5 ) and the PVDF binder were weighed so that the PVDF binder became 1 mass part with respect to 100 weight parts of the sulfide solid electrolyte, they were blended so that the solid content became 63 mass %, and they were kneaded for 1 minute using the ultrasonic sound wave homogenizer to prepare a separator composition in a slurry state. Afterwards, the separator composition in the slurry state was applied on the surface of the aluminum foil and underwent the process of drying by heating to form a separator layer. Next, the separator layer was transferred to the cathode structure and had the anode structure further transferred to prepare the separator layer and a battery cell. 
     [Evaluation] 
     The batteries obtained in Working example 1 to Working example 5, Comparative example 1, and Comparative example 2 were charged and discharged for 500 cycles by from 3.0 V to 4.2 V, and resistance values at the 500th cycle were defined as post-cycle resistance values. Here, the resistance value was obtained from a voltage difference (ΔV) when the battery was discharged for 1 second from SOC (state of charge) 20% at 4C (C rate). Then, by defining the post-cycle resistance value of Working example 3 as 1.0, the ratio to the post-cycle resistance value of each example (post-cycle resistance ratio) was obtained. Table 1 shows the result. Further,  FIG. 3  shows a graph representing V V1 /V V2  on the horizontal axis and the post-cycle resistance ratio on the vertical axis. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 (Table 1) 
               
            
           
           
               
               
               
               
            
               
                   
                   
                   
                 Post-cycle 
               
               
                   
                   
                 V V1 /V V2   
                 resistance ratio 
               
               
                   
                   
               
               
                   
                 Working example 1 
                 5.0 
                 1.05 
               
               
                   
                 Working example 2 
                 3.0 
                 1.01 
               
               
                   
                 Working example 3 
                 1.5 
                 1.00 
               
               
                   
                 Working example 4 
                 1.0 
                 1.01 
               
               
                   
                 Working example 5 
                 0.8 
                 1.02 
               
               
                   
                 Comparative example 1 
                 7.0 
                 1.09 
               
               
                   
                 Comparative example 2 
                 0.5 
                 1.08 
               
               
                   
                   
               
            
           
         
       
     
     As Table 1 and  FIG. 3  suggest, the post-cycle resistance ratio was able to be reduced by setting V V1 /V V2  to be from 0.8 to 5.0. 
     DESCRIPTION OF REFERENCE SIGNS 
     
         
           10  All-solid battery 
           11  Cathode layer 
           12  Anode layer 
           13  Solid electrolyte layer 
           14  Cathode current collector 
           15  Anode current collector