JP2016031782A - All-solid type secondary battery and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an all-solid type secondary battery arranged with a material which makes easier to check the sinterability of a solid electrolyte.SOLUTION: An all-solid type secondary battery 1 comprises: a laminate part arranged by laminating a positive electrode layer 31 and a negative electrode layer 32 through a solid electrolytic layer 21; and a protection layer 11, 12 formed on at least one side of the laminate part and including a solid electrolyte. In colorimetry/color-difference measurement in which presentation is made by L*a*b*color system, the protection layer 11, 12 shows a color value L* of 10-90 and a chroma (a*×a*+b*×b*)of 10 or larger. A method for manufacturing an all-solid type secondary battery comprises the steps of: manufacturing a green sheet of a solid electrolyte; forming a positive electrode layer on the green sheet; forming a negative electrode layer on the green sheet; laminating the green sheet which will make a protection layer 11, 12; manufacturing a pre-baking block; and baking the pre-baking block. In the method, the green sheet which will make the protection layer 11, 12 includes at least one element selected from V, Cr, Mn, Fe, Co, Ni, Cu and B.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an all-solid secondary battery having a solid electrolyte and a method for manufacturing the same.

  In recent years, lithium-ion secondary batteries and electric double layer capacitors have been actively developed as large-capacity electrochemical devices, and have begun to be used in various fields such as consumer equipment, industrial machinery, and automobiles. Properties required for electrochemical devices include high energy density, high power density, and high capacity and high responsiveness. Furthermore, since there are cases such as ignition accidents, sophistication is also required for safety in electrochemical devices. In particular, accidents in in-vehicle and medical electrochemical devices are directly related to human life, and therefore higher safety is required. One of the causes of ignition accidents in electrochemical devices is that flammable liquids called electrolytes are contained inside. There is a demand for a device that does not rupture or ignite even in an unforeseen situation, and in recent years, it has been desired to make an electrochemical device completely solid.

In Patent Document 1, Li _{1 + x + z} M _x (Ge _1−y Ti _y ) _2−x Si _z P _3−z O ₁₂ (provided that 0 ≦ ≤) is a crystal having lithium ion conductivity as an example of a solid electrolyte material. x ≦ 0.8, 0 ≦ y ≦ 1.0, 0 ≦ z ≦ 0.6, M = one or more selected from Al and Ga).

JP 2011-86610 A

  In an all-solid secondary battery, it is important to adjust the degree of sintering in the production of the solid electrolyte. This is because insufficient sintering can cause deterioration in reliability, and excessive sintering can cause reduction in capacity. However, it is not easy to check the sinterability one by one in the mass production process.

  In view of the above, an object of the present invention is to provide an all-solid-state secondary battery using a material that easily checks the sinterability of a solid electrolyte and a method for manufacturing the same.

According to the present invention, the all-solid-state secondary battery includes a laminated portion in which a positive electrode layer and a negative electrode layer are laminated via a solid electrolyte layer, and a protection comprising a solid electrolyte formed in at least one of the laminated portions. Having a layer. In the color difference measurement expressed in the L * a * b * color system, the protective layer has a lightness L * of 10 or more and 90 or less and a saturation of 10 or more (a * × a * + b * × b *) ^1/2 Presents. Preferably, the protective layer contains at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu and B.

  According to the manufacturing method of the present invention, a solid electrolyte green sheet is manufactured, a positive electrode layer is formed on the green sheet, a negative electrode layer is formed on the green sheet, the green sheet serving as a protective layer is laminated, and fired An all-solid-state secondary battery is obtained by manufacturing the front block and firing the pre-fired block. In the production method of the present invention, the green sheet serving as the protective layer contains at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, and B.

  According to the present invention, since the sinterability (density) of the solid electrolyte can be determined from the color tone of the outer appearance of the protective layer, it can be determined from the appearance that the sintering is appropriate without deteriorating the characteristics of the secondary battery. . According to the preferred embodiment, a material having a predetermined brightness and hue that enables sinterability evaluation by color tone without changing the crystal structure of the solid electrolyte is obtained, and the storage capacity of the secondary battery is not reduced.

It is a schematic cross section of the all-solid-state secondary battery of the present invention. It is an example of the X-ray diffraction pattern of solid electrolyte material. It is an example of the color difference measurement result of a solid electrolyte material. It is an example of the color difference measurement result of a solid electrolyte material.

The present invention will be described in detail with appropriate reference to the drawings. However, the present invention is not limited to the illustrated embodiment, and in the drawings, the characteristic portions of the invention may be emphasized and expressed, so that the accuracy of the scale is not necessarily guaranteed in each part of the drawings. Not.
FIG. 1 is a schematic cross-sectional view of an all solid state secondary battery according to the present invention. The all-solid-state secondary battery 1 has a stacked structure in which a positive electrode layer 31 and a negative electrode layer 32 (both are collectively referred to as an electrode layer) are stacked vertically with a solid electrolyte layer 21 interposed therebetween. “Laminated up and down” means in the present invention that the stacking direction is defined as the up-and-down direction, and does not limit the manufacturing method of the stacked structure, but limits the directionality during mounting. Nor is it intended. Further, it is not necessary to determine which is the top and which is the bottom.

As a typical stack unit of the all-solid-state secondary battery 1, a stack structure of positive electrode layer 31 / solid electrolyte layer 21 / negative electrode layer 32 / solid electrolyte layer 21 can be given. The all-solid-state secondary battery 1 may have only one of these stack units, or may preferably have a plurality of stack units, preferably about 10 to 200 units. The above-mentioned lamination unit or a lamination structure by repetition thereof is referred to as a lamination portion. Protective layers 11 and 12 made of a solid electrolyte are provided on at least one of the upper and lower sides of the laminated portion, preferably both. In the illustrated embodiment, the positive electrode layer 31 is connected to the first external electrode 41 provided on one side surface (the left side in FIG. 1) of the all-solid-state secondary battery 1, and the negative electrode layer 32 is all-solid-state. The secondary battery 1 is connected to a second external electrode 42 provided on a side surface opposite to the external electrode 41 (right side in FIG. 1). For the overall laminated structure and the structure of the external electrodes 41 and 42, the prior art in all-solid secondary batteries can be referred to as appropriate.
That is, it has a laminated part in which a positive electrode layer and a negative electrode layer are laminated via a solid electrolyte layer, and a protective layer made of a solid electrolyte formed in at least one of the laminated parts. The first external electrode is connected to the positive electrode layer, and the second external electrode is connected to the negative electrode layer. In one embodiment, the positive electrode layer is composed of a collector electrode and a positive electrode active material layer, and the negative electrode layer is composed of a collector electrode and a negative electrode active material layer. In the embodiment, protective layers are formed on both surfaces of the laminated portion.

  The solid electrolyte of the protective layers 11 and 12 may be a different material from the solid electrolyte layer 21 in the laminated portion, or may be a homogeneous material. When the solid electrolytes of the protective layers 11 and 12 and the solid electrolyte layer in the laminated portion have the same composition, the shrinkage of the fired characters is the same, and thus cracks are less likely to occur. In this case, the same element as the solid electrolyte of the protective layers 11 and 12 may also be contained in the solid electrolyte layer in the laminated portion.

The solid electrolytes of the protective layers 11 and 12 and the solid electrolyte layer 21 are preferably made of a phosphate having a NASICON structure containing lithium. Such phosphates are conventionally known as materials for solid electrolytes, and can be used without any particular limitation. Typical examples include, for example, composite lithium phosphate with Ti, and metal elements such as Al, Ge, Sn, Hf, Zr, Y, La, etc. are used in place of or added to the Ti. It is also possible. Al may be substituted with other trivalent transition metals such as Ga, In, and La. More specifically, examples of the phosphate having a NASICON structure containing lithium include the following compositions.
LiTi ₂ (PO ₄ ) ₃ ,
Li _{(1 + x)} Al _x Ti _(2-x) (PO ₄ ) ₃ (0 ≦ x ≦ 2, LATP) and the like.

  The formation method of the solid electrolyte layer 21 is not particularly limited, and the prior art can be referred to as appropriate. For example, the above-mentioned phosphate material is prepared so as to have an appropriate particle size distribution, and is uniformly dispersed in an aqueous solvent or an organic solvent together with a binder, a dispersant, a plasticizer, and the like to obtain a slurry. At this time, a bead mill, a wet jet mill, various kneaders, a high-pressure homogenizer, and the like can be used. Among them, the use of a bead mill is preferable because the particle size distribution can be adjusted and dispersed at the same time. The obtained slurry is applied to obtain a green sheet having a desired thickness. The coating method is not particularly limited, and the prior art can be referred to as appropriate. Examples thereof include a slot die method, a reverse coating method, a gravure coating method, a bar coating method, and a doctor blade method.

  At least one of the protective layers 11 and 12 preferably has a lightness L * of 10 to 90. If it exceeds 90, white will be too strong and it will be difficult to distinguish the color difference, and if it is less than 10, black will be too strong and it will be difficult to distinguish the color difference. More preferably, it is 20-80. The saturation C * is preferably 20 or more. If the saturation C * is less than 20, the color becomes too dull and it is difficult to distinguish the color difference. Preferably, it is 40 or more. The L * value and the C * value are parameters based on the L * a * b * color system described below.

The L * a * b * color system is a standard specification for representing the color of an object (JIS Z8781-4: 2013). In the L * a * b * color system, lightness is represented by L *, and chromaticity indicating hue and saturation is represented by a * and b *. a * and b * indicate the color direction, a * indicates the red direction, -a * indicates the green direction, b * indicates the yellow direction, and -b * indicates the blue direction. The higher the value, the brighter the color, and the smaller the value, the dull color. The magnitudes of the absolute values in the a * direction and b * direction are parameters related to the vividness of the color. In the present invention, the brightness L * value and (a * × a * + b * × b *) ^1/2 Focus on the value (also referred to herein as the saturation C * value).

  Although the values of L *, a *, and b * are not of a property that can be controlled completely independently, in general, it is effective to increase the addition amount of a transition metal or the like in order to lower the L * value. In order to control the a * value and the b * value, it is effective to change the type of transition metal or the like.

  When a transition metal such as V, Cr, Mn, Fe, Co, Ni, Cu or B is added to a phosphate containing lithium and having a NASICON structure and sintered, it can be colored. In most cases, as the firing temperature is increased, both an increase in the sintered density and a change in the color of the sintered body are observed, and a correlation close to proportionality is established between the sintered density and the color parameter. The greater the change in color parameter relative to the change in sintering density, the easier it is to manage the sintering. Furthermore, it is preferable that the color parameter near the target sintered density is not an extreme value. The extreme value referred to here is when the lightness L * is less than 10, or when the value is more than 90 or when the saturation C * is less than 20. When the temperature fluctuates on the low temperature side, reliability is deteriorated and characteristics deteriorate due to insufficient sintering. Further, when the temperature fluctuates on the high temperature side, capacity reduction and characteristic deterioration occur due to oversintering, interaction between different materials and abnormal grain growth. Color parameters that can infer such defects from the appearance are preferred.

The lightness L * is preferably 20 or more and 80 or less, and the saturation (a * × a * + b * × b *) ^1/2 is preferably 20 or more. The saturation (a * × a * + b * × b *) ^1/2 is more preferably 40 or more. The change rates of the sintered density (Density), lightness L * (L * value), and saturation C * (C * L * value) are ΔD, ΔL *, and ΔC *. Specifically, as a correlation between the sintered density and the color parameter, the absolute value of the ratio ΔL * / ΔD of the change rate ΔL * of the lightness L * and the change rate ΔD of the sintered density D, and the change rate ΔC of the saturation C * The absolute value of the ratio ΔC * / ΔD between * and ΔD is preferably 10 or more (that is, ΔL * / ΔD is 10 or more and ΔC * and ΔD are 10 or more). If these ratios are less than 10, the color parameters hardly change even if the sintering density D changes, so that the degree of sintering cannot be judged. More preferably, both of these ratios are 20 or more, and in this case, the difference can be identified visually (that is, ΔL * / ΔD is 20 or more, and ΔC * and ΔD are 20 or more).

  By substituting a part of the site such as Ti site by doping with another transition metal or the like, it can be adjusted to a material exhibiting a visible color. The transition metal may be added at the synthesis stage of LATP or the like, or may be added at the time of blending the slurry when applying a green sheet such as LATP after synthesis. When the coating method is changed for the solid electrolyte layer and the protective layer, a transition metal or the like may be added separately only for the protective layer. Further, in consideration of the addition amount, the ratio of the other constituent elements may be the stoichiometric composition as a whole, or a transition metal may be additionally added to LATP or the like of the stoichiometric composition.

  The addition amount of another transition metal or the like is preferably as small as possible in order to eliminate the influence on the characteristics as much as possible. In particular, it is not preferable to add the solid electrolyte layer and the protective layer in the laminated portion so that the shrinkage ratios are significantly different, because cracks and delamination are induced during chip firing. The generation of the secondary phase due to the addition is less likely to be a problem because only the protective layer has little effect on the characteristics. From the above, the amount generally added is preferably 0.005 to 0.5 mol and more preferably 0.01 to 0.25 mol with respect to 1 mol of the total amount of Ti and Al. According to the present invention, the transition metal element of the fourth period, particularly the Group 5 to 11 is particularly effective as an element that exhibits a visible color in a relatively small amount. On the other hand, the transition metal element in the fifth period tends not to exhibit color.

  Examples of the element preferably added to the protective layers 11 and 12 include at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, and B. Addition of these elements does not change the crystal structure of the solid electrolyte, so that a reduction in the storage capacity of the secondary battery can be suppressed, and the above-described brightness and hue can be obtained.

  The positive electrode layer 31 and the negative electrode layer 32 typically include a stacked structure in which a current collector layer (not shown) is sandwiched between two active material layers.

  For the active material of the electrode, the prior art in the secondary battery can be referred to as appropriate. For example, as the positive electrode active material, lithium manganese composite oxide, lithium nickel composite oxide, lithium cobalt composite oxide, lithium nickel cobalt composite oxide, lithium manganese nickel composite compound, spinel type lithium manganese nickel composite oxide, lithium manganese cobalt You may use powder, such as complex oxide and lithium iron phosphate. As the negative electrode active material, powders of titanium oxide, lithium-titanium composite oxide, carbon, lithium vanadium phosphate, and the like may be used. In addition to these active materials, a solid electrolyte material or a conductive material such as carbon or metal may be further used. A positive (negative) electrode active material layer paste can be obtained by uniformly dispersing these members, binder and plasticizer in water or an organic solvent.

  Examples of the conductive metal of the current collector include, but are not limited to, simple metals, alloys, or oxides of metals such as Ni, Cu, Pd, Ag, Pt, Au, Al, and Fe. By using the positive (negative) electrode active material layer paste and the current collector conductive metal paste, the precursors of the positive electrode layer 31 and the negative electrode layer 32 can be formed. As an example of the forming method, a positive (negative) active material layer paste is printed on the above-described green sheet for a solid electrolyte layer, then a conductive metal paste is printed, and then a positive ( By printing the negative active material layer, a laminated structure of positive (negative) active material layer / collector electrode / positive (negative) active material layer can be produced. The printing method is not particularly limited, and conventionally known printing methods such as a screen printing method, an intaglio printing method, a relief printing method, and a calendar roll method can be applied. Screen printing is considered to be the most common method for producing a thin and highly laminated device. On the other hand, if very fine electrode patterns or special shapes are required, it may be preferable to apply ink jet printing.

  Known techniques can be referred to as appropriate for the production of the laminate. Typically, a green sheet for the solid electrolyte layer 21 formed by printing the above-described laminated structure for the positive electrode and the negative electrode is appropriately laminated, and is pressure-bonded by various methods to obtain a laminated body (precursor of a laminated portion). Get. The green sheets for the protective layers 11 and 12 are laminated on at least one of the upper and lower sides of the laminate. In this way, a block before firing is obtained. The external electrodes 41 and 42 are formed as necessary, or after cutting into a chip shape, the pre-fired block is fired. The firing conditions are an oxidizing atmosphere or a non-oxidizing atmosphere, and the maximum temperature is preferably 400 ° C to 1000 ° C, more preferably 500 ° C to 900 ° C. The holding time at the maximum temperature is preferably 10 min to 10 hr, more preferably 30 min to 5 hr, and further preferably 1 hr to 3 hr. If the holding is performed for a short time, there is a concern about uneven firing inside and outside the structure, and if the holding time is too long, the productivity is deteriorated and the process cost is increased. In order to sufficiently remove the binder before reaching the maximum temperature, a step of maintaining the temperature lower than the maximum temperature in an oxidizing atmosphere may be provided. In order to reduce the process cost, it is desirable to fire at as low a temperature as possible. A re-oxidation treatment may be performed after firing. In this way, the all solid state secondary battery of the present invention is obtained. Preferably, at least one element selected from the group consisting of a phosphate containing lithium and having a NASICON structure, and V, Cr, Mn, Fe, Co, Ni, Cu, and B is included in the green sheet for the protective layer. And include.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the embodiments described in these examples.

[Production Example 1]
Li ₂ CO ₃ , α-Al ₂ so that the molar ratio is 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.017V ₂ O ₅ /1.5P ₂ O ₅ O ₃ , anatase-type TiO ₂ , NH ₄ H ₂ PO ₄ , and V ₂ O ₅ are mixed and calcined at 850 ° C. in the atmosphere to cause a solid-phase reaction to obtain a solid electrolyte V-LATP powder (powder) 1) was obtained. The obtained powder 1 was evaluated by the powder XRD method. FIG. 2 shows a diffraction pattern obtained by the above evaluation, and the pattern of the powder 1 is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 1 was yellow.

[Production Example 2]
Solid electrolyte as in Production Example 1 except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.034 MnO ₂ /1.5P ₂ O ₅ A powder of Mn-LATP (powder 2) was obtained. Here, MnCO ₃ was used as a raw material for Mn. A diffraction pattern of the obtained powder 2 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 2 was light purple.

[Production Example 3]
The solid electrolyte Co was prepared in the same manner as in Production Example 1 except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.2CoO/1.5P ₂ O _5. A powder of LATP (powder 3) was obtained. Here, (CH ₃ COO) ₂ Co.4H ₂ O was used as a raw material for Co. A diffraction pattern of the obtained powder 3 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON type crystal structure was observed and was almost a single phase, but a secondary phase was slightly confirmed by increasing the addition amount. The color of the powder 3 was purple.

[Production Example 4]
Solid electrolyte Ni in the same manner as in Production Example 1 except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.2NiO/1.5P ₂ O _5. A powder of LATP (powder 4) was obtained. Here, NiO was used as a Ni raw material. A diffraction pattern of the obtained powder 4 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON type crystal structure was observed and was almost a single phase, but a secondary phase was slightly confirmed by increasing the addition amount. The color of the powder 4 was yellow.

[Production Example 5]
Mol _{0.65Li 2 O / 0.15Al 2 O 3} /1.7TiO 2 /0.034CuO/1.5P 2 O 5 addition to were mixed at a ratio of at terms in the same manner as in Example 1 the solid electrolyte Cu A powder of LATP (powder 5) was obtained. Here, CuO was used as a Cu raw material. A diffraction pattern of the obtained powder 5 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 5 was greenish white.

[Production Example 6]
The same as Production Example 1 except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.017B ₂ O ₃ /1.5P ₂ O ₅ A solid electrolyte B-LATP powder (powder 6) was obtained. Here, H ₃ BO ₃ was used as a raw material for B. A diffraction pattern of the obtained powder 6 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 6 was yellowish white.

[Production Example 7]
The solid electrolyte LATP powder (as in Production Example 1) except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /1.5P ₂ O ₅ A powder 7) was obtained. A diffraction pattern of the obtained powder 7 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 7 was white.

[Production Example 8]
The same as Production Example 1 except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.017 Nb ₂ O ₅ /1.5P ₂ O _5. A solid electrolyte Nb-LATP powder (powder 8) was obtained. Here, Nb ₂ O ₅ was used as a raw material for Nb. A diffraction pattern of the obtained powder 8 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 8 was white.

[Production Example 9]
The solid electrolyte was the same as in Production Example 1 except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.034 SnO ₂ /1.5P ₂ O _5. Sn-LATP powder (powder 9) was obtained. Here, SnO ₂ was used as a raw material of Sn. A diffraction pattern of the obtained powder 9 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 9 was white.

[Production Example 10]
The solid electrolyte was the same as in Production Example 1 except that it was mixed in a molar ratio of 0.65Li ₂ O / 0.15Al ₂ O ₃ /1.7TiO ₂ /0.034 MoO ₃ /1.5P ₂ O _5. Mo-LATP powder (powder 10) was obtained. Here, MoO ₃ was used as a Mo raw material. A diffraction pattern of the obtained powder 10 by the powder XRD method is shown in FIG. As shown in the figure, a diffraction peak attributed to the NASICON crystal structure was observed, and it was confirmed that it was almost single phase. The color of the powder 10 was white.

[Example 1]
Using the above-mentioned solid electrolyte Co-LATP powder (powder 3), a chip-shaped all-solid battery was produced. A green sheet for a solid electrolyte was prepared using the powder 3, and a composite paste of Pd, LiCoPO ₄ and a solid electrolyte was pattern printed as a positive electrode layer, and a Pd current collector paste was printed in a similar pattern thereon. Thereafter, a Pd—LiCoPO ₄ composite paste was again printed thereon with a similar pattern. A Pd paste was printed as a negative electrode layer separately on the solid electrolyte green sheet. The negative electrode active material uses oxidation reduction (Ti ⁴⁺ → Ti ³⁺ ) of Ti contained in the solid electrolyte. The printing pattern at this time was a pattern in which the positive electrode layer and the lead-out portion were different. Prepare 15 sheets of green sheets printed with the positive electrode layer and 16 green sheets printed with the negative electrode layer, and laminate them alternately in the form of negative electrode, positive electrode, negative electrode, positive electrode, and so on. The above-mentioned green sheets for the solid electrolyte using the powder 3 were stacked as protective layers on the upper and lower sides, respectively, to form a pressure-bonded sheet. One sheet of Pd paste printed with a positive electrode pattern on the outer side of the protective layer was laminated so that the electrode printing surface was on the inner side. This is so that the positive electrode side of the manufactured chip can be seen visually. The layers laminated in the order of the protective layer, the laminated portion, and the protective layer were pressure-bonded at 120 ° C. and 40 MPa by an isostatic press, and cut into chips so that a positive electrode lead portion and a negative electrode lead portion were formed. This chip was fired in the atmosphere at 830 ° C. for 3 hours to obtain a laminated chip type all solid lithium ion secondary battery.
It was confirmed that the chip after firing had a purple appearance and could be charged and discharged. The chip size at this time was about 5 mm square. A color difference measurement was performed on the protective layer of this chip to obtain an L * value of 67.32, an a * of 24.01 and a b * value of −19.43 (ie, the C * value is 30.89). .)

Separately, the sintering temperature was further increased to 930 ° C. to change the sintering condition, and a chip having a darker purple appearance was obtained. In this chip, it was considered that the positive electrode active material reacted with the solid electrolyte, and a decrease in capacity was confirmed. A color difference measurement was performed on the protective layer of this chip to obtain an L * value of 51.24, an a * of 31.22 and a b * value of −23.14 (ie, the C * value is 38.86). .) Thus, the possibility that overburning due to a defect in the firing process can be distinguished from the appearance was shown. The difference in appearance color between the 830 ° C. fired chip and the 930 ° C. fired chip could be clearly recognized visually.

[Reference Experiment 1]
Forty green sheets of the above-mentioned solid electrolyte Co-LATP powder (powder 3) were laminated and pressure-bonded, then punched out to 17 mm and fired at 700 to 900 ° C. in the atmosphere at a plurality of temperatures. The density of each disc after firing was measured. Moreover, the color of the disk was measured by the L * a * b * method using a color difference meter. The relationship between the density of the disc and each parameter obtained from the color difference meter was plotted. FIG. 3 shows the plot. 3 (a), (b), (b), L * value representing lightness, a * value representing chromaticity in the red / green direction, b * value representing yellow / blue direction, and C * value representing saturation. Shown in c) and (d), respectively. According to these figures, it can be confirmed that each parameter of the color changes greatly with respect to the change of the disk density. Therefore, it is possible to know the disk density, that is, the degree of sintering by measuring the color. With this level of parameter change, it is possible to confirm a change in color due to an increase in disc density even by visual observation. By quantifying the appearance color of the product in this way, by investigating the correlation with the densification level in advance, it can be used as an indicator of the degree of densification in firing, and nondestructive and non-contact in the firing process. It can be a powerful tool for process management.

[Reference Experiment 2]
After 40 green sheets of the above-mentioned solid electrolyte LATP powder (powder 7) were laminated and pressure-bonded, they were punched to 17 mm and fired at 650 ° C. to 950 ° C. in the atmosphere at a plurality of temperatures. The density of each disc after firing was measured. Moreover, the color of the disk was measured by the L * a * b * method using a color difference meter. The relationship between the density of the disc and each parameter obtained with the color difference meter is plotted. FIG. 4 shows the plot. As in FIG. 3, the L * value, a * value, b * value, and C * value are shown in FIGS. 4 (a), (b), (c), and (d), respectively. According to these figures, it can be confirmed that each parameter of the color hardly changes with the change of the disc density. Therefore, it is impossible to know the disk density, that is, the degree of sintering even if the color is measured. With this level of parameter change, it was impossible to confirm the color change accompanying the increase in the disk density even by visual observation, and the color was all white and almost no difference could be recognized.

DESCRIPTION OF SYMBOLS 1 All-solid-state secondary battery 11, 12 Protective layer 21 Solid electrolyte layer 31 Positive electrode layer 32 Negative electrode layer 41, 42 External electrode

Claims (3)

A laminated portion in which a positive electrode layer and a negative electrode layer are laminated via a solid electrolyte layer, and a protective layer made of a solid electrolyte formed in at least one of the laminated portions,
In the color difference measurement expressed in the L * a * b * color system, the protective layer has a lightness L * of 10 or more and 90 or less and a saturation of 10 or more (a * × a * + b * × b *) ^1/2 Presenting,
All-solid secondary battery.   The all-solid-state secondary battery according to claim 1, wherein the protective layer contains at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, and B. Manufacturing solid electrolyte green sheets,
Forming a positive electrode layer on the green sheet;
Forming a negative electrode layer on the green sheet;
Laminating the green sheet to be a protective layer, producing a block before firing,
Having the step of firing the block before firing,
The green sheet serving as the protective layer includes at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu and B.
Manufacturing method of all-solid-state secondary battery.

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