JP2010245039A - All solid lithium battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an all-solid lithium battery superior in output characteristics. <P>SOLUTION: As for the all-solid lithium battery, the positive electrode contains a positive electrode active material as expressed by the following formula (1) and a sulfide system solid electrolyte, and an electrolyte layer contains the sulfide system solid electrolyte. Formula (1): Li<SB>a</SB>Ni<SB>b</SB>Co<SB>c</SB>Mn<SB>d</SB>M<SB>e</SB>O<SB>f+σ</SB>. In the formula, a is a number to satisfy 1.01≤a≤1.05, f is 2 or 4, σ is -0.2 or more and 0.2 or less, M is one kind or more element selected from Mg, Ca, Y, rare earth element, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Cu, Ag, Zn, B, Al, Ga, C, Si, Sn, N, P, S, F, and Cl. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an all-solid lithium battery.

  For lithium batteries using flammable organic solvent electrolytes, concerns about their safety, such as ignition, are an essential problem. A fundamental solution to this safety problem is to use a non-flammable electrolyte instead of a flammable organic solvent electrolyte.

  A typical example of the nonflammable electrolyte is a lithium ion conductive solid electrolyte which is an inorganic substance. By using an inorganic solid electrolyte, not only can safety be improved, but the battery can be thinned and integrated with an electronic circuit, and since the inorganic solid electrolyte has ion selectivity, cycle life, storage life, etc. The reliability of the battery can also be improved.

  Many of the causes of capacity reduction and self-discharge associated with charge / discharge cycles are side reactions occurring in the battery. Among lithium batteries, the only ions that contribute to the electrode reaction of lithium ion batteries are lithium ions.

  In a lithium battery using an organic solvent electrolyte, in the liquid electrolyte, anions, solvent molecules, impurities, and the like move, and if these diffuse to the surface of the positive electrode having a high oxidizing power or the negative electrode having a high reducing power, they are oxidized or reduced. May be. There was a problem that such a side reaction caused deterioration of battery characteristics.

  In contrast, in a lithium battery using an inorganic solid electrolyte, since the inorganic solid electrolyte has ion selectivity, only lithium ions move in the inorganic solid electrolyte. Therefore, unlike a lithium battery using an organic solvent electrolyte, side reactions do not continue due to diffusion of components other than lithium ions to the electrode surface. Therefore, an all-solid battery using an inorganic solid electrolyte is a battery having a long life and low self-discharge.

  Examples of the all-solid battery include an all-solid lithium secondary battery (Patent Document 1) using a carbon material having a low potential and a high capacity density as a negative electrode material, an all-solid lithium secondary battery having a high energy density, and the like. The output density obtained in the all-solid lithium secondary battery was about several hundred microamperes per square centimeter, which was still lower than that of the liquid electrolyte battery. That is, the all-solid lithium secondary battery has excellent reliability such as safety, but generally has a problem that its energy density or output density is lower than that of a liquid electrolyte battery.

International Publication No. 2007/004590 Pamphlet

  An object of the present invention is to provide an all solid lithium battery having excellent output characteristics.

According to the present invention, the following all solid lithium battery is provided.
The all solid lithium battery of the present invention comprises a positive electrode, an electrolyte layer and a negative electrode,
The positive electrode includes a positive electrode active material represented by the following formula (1) and a sulfide-based solid electrolyte, and the electrolyte layer includes a sulfide-based solid electrolyte.
Li _a Ni _b Co _c Mn _{d Me} O _{f + σ} (1)
(Wherein, a is a number satisfying 1.01 ≦ a ≦ 1.05,
f is 2 or 4, σ is −0.2 or more and 0.2 or less, M is Mg, Ca, Y, rare earth element, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W , Fe, Cu, Ag, Zn, B, Al, Ga, C, Si, Sn, N, P, S, F, and Cl.
When f is 2, b is a number satisfying 0 ≦ b ≦ 1, c is a number satisfying 0 ≦ c ≦ 1, d is a number satisfying 0 ≦ d ≦ 1, and e is 0 ≦ e It is a number satisfying ≦ 0.5, and b + c + d + e = 1.
When f is 4, b is a number that satisfies 0 ≦ b ≦ 2, c is a number that satisfies 0 ≦ c ≦ 2, d is a number that satisfies 0 ≦ d ≦ 2, and e is 0 ≦ e It is a number satisfying ≦ 1, and b + c + d + e = 2. )
The positive electrode active material is Li _a CoO _{2 + σ} , Li _a Ni _{0.8 ± 0.1} Co _{0.15 ± 0.1} Al _{0.05 ± 0.05} O _{2 + σ} , Li _a Ni _{0.8 ± 0.1} Co _{0.2 ± 0.1} O _{2 + σ} , Li _a NiO _{2 + σ} , Li _a Mn ₂ O ₄ , Li _a Mn _0.5 Ni _0.5 O ₂ , Li _a Mn _1.5 Ni _0.5 O ₄ , or Li _a Mn _1/3 Ni _1/3 Co _1/3 O ₂ is preferable.
It is preferable that a is a number satisfying 1.01 ≦ a ≦ 1.04.

  According to the present invention, an all-solid lithium battery excellent in output characteristics can be provided.

It is a schematic sectional drawing which shows one Embodiment of the all-solid-state lithium battery of this invention.

The all solid lithium battery of the present invention includes a positive electrode, an electrolyte layer, and a negative electrode, the positive electrode includes a positive electrode active material represented by the following formula (1) and a sulfide solid electrolyte, and the electrolyte layer is a sulfide solid electrolyte. including.
Li _a Ni _b Co _c Mn _{d Me} O _{f + σ} (1)
(Wherein, a is a number satisfying 1.01 ≦ a ≦ 1.05,
f is 2 or 4, σ is −0.2 or more and 0.2 or less, M is Mg, Ca, Y, rare earth element, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W , Fe, Cu, Ag, Zn, B, Al, Ga, C, Si, Sn, N, P, S, F, and Cl.
When f is 2, b is a number satisfying 0 ≦ b ≦ 1, c is a number satisfying 0 ≦ c ≦ 1, d is a number satisfying 0 ≦ d ≦ 1, and e is 0 ≦ e It is a number satisfying ≦ 0.5, and b + c + d + e = 1.
When f is 4, b is a number that satisfies 0 ≦ b ≦ 2, c is a number that satisfies 0 ≦ c ≦ 2, d is a number that satisfies 0 ≦ d ≦ 2, and e is 0 ≦ e It is a number satisfying ≦ 1, and b + c + d + e = 2. )

σ is a value that balances charges, determined by the contents of Li, Ni, Co, Mn, and M, and the type of M, and σ is in the range of −0.2 to 0.2. For convenience, the value of σ is described as 0 in the present application.
The positive electrode active material of the present invention does not necessarily contain M, but can be contained for the purpose of improving various battery characteristics, or may be contained as an unavoidable impurity. When Ti is included as M, the load characteristic is improved because the speed of deintercalation or intercalation of Li during charge / discharge is increased. When M is Mg or Al, thermal stability is improved by stabilizing the crystal structure. In addition, there is an effect of promoting the diffusion and reaction of Li when synthesizing the positive electrode active material. When M is Zr or Hf, charging and discharging at a high potential becomes possible by stabilizing the crystal structure.

When the positive electrode active material represented by the above formula (1) (hereinafter sometimes referred to as the positive electrode active material of the present invention) is, for example, Li _a CoO ₂ , battery performance can be improved. The reason for this is not clear, but Li _a CoO ₂ contains more Li ions than LiCoO ₂ , so that Li can be diffused smoothly at the interface between Li _a CoO ₂ and the sulfide-based solid electrolyte. It is presumed that the crystallinity of Li _a CoO ₂ is increased, the mechanical strength of the particles is improved, and the particles are less likely to be collapsed at the time of electrode preparation.
However, when a is more than 1.05, Li _a CoO ₂ may not function as a positive electrode active material because the crystal structure is not stabilized.

The positive electrode active material of the present invention are preferably _{Li a CoO 2 + σ, Li} a Ni 0.8 ± 0.1 Co 0.15 ± 0.1 Al 0.05 ± 0.05 O 2 + σ, Li a Ni 0.8 _{± 0.1} Co _{0.2 ± 0.1} O _{2 + σ} , Li _a NiO _{2 + σ} , Li _a Mn ₂ O ₄ , Li _a Mn _0.5 Ni _0.5 O ₂ , Li _a Mn _1.5 Ni _0.5 O ₄ , or Li _a Mn _1/3 Ni _1/3 Co _1/3 O ₂ .

A in the positive electrode active material of the present invention is preferably a number satisfying 1.01 ≦ a ≦ 1.04.
By setting a in the above range, the positive electrode active material of the present invention contains a large amount of Li ions and has a stable crystal structure, so that the battery performance can be improved.

The particle size of the positive electrode active material of the present invention is preferably 0.1 to 20 μm, more preferably 0.1 to 15 μm, and further preferably 0.1 to 10 μm.
In addition, the said particle size is the value of D50 measured by the laser diffraction method.

The BET surface area of the positive electrode active material of the present invention is preferably 0.1 to 1.0 m ² / g.
The BET surface area can be measured, for example, by the N ₂ adsorption BET method using NOVA2000 (manufactured by Kantachrome) after degassing the positive electrode active material to be measured at 200 ° C. for 20 minutes.

For example, Li _a CoO ₂ that is the positive electrode active material of the present invention can be produced by the following method.
Cobalt hydroxide by adding an aqueous solution of a cobalt compound such as an aqueous cobalt sulfate solution and an aqueous cobalt nitrate solution and an alkaline aqueous solution such as an aqueous sodium hydroxide solution and an aqueous ammonia solution to the reaction vessel while stirring while controlling the temperature and pH. Is obtained.
For example, an ammonium salt complexing agent such as ammonium sulfate or ammonium nitrate may be suitably added to the reaction vessel.

Cobalt oxide can be obtained by baking the obtained cobalt hydroxide at 300 ° C. to 850 ° C. for 1 to 24 hours. And mixed further added lithium carbonate, _Li a CoO ₂ is obtained by firing at 850 ° C. to 1050 ° C.. Firing may be pre-baked at a temperature lower than the target baking temperature, and then heated to the target baking temperature.

The concentration of the aqueous solution of the cobalt compound, the concentration of the aqueous alkali solution, addition rates, pH, temperature, the concentration of the complexing agent and the like, or by the resulting firing conditions cobalt hydroxide, Li _a CoO ₂ shape, particle size And the particle size distribution can be controlled.

  As the sulfide-based solid electrolyte contained in the positive electrode, a sulfide-based solid electrolyte consisting only of sulfur, phosphorus and lithium can be used, and the sulfide-based solid electrolyte may further contain Al, B, Si, Ge, etc. Good.

The sulfide-based solid electrolyte can be produced by using, as a raw material, a material composed of an organic compound, a material composed of an inorganic compound, or a material composed of an organic compound and an inorganic compound.
Specifically, lithium sulfide (Li ₂ S) and diphosphorus pentasulfide (P ₂ S ₅ ); lithium sulfide, simple phosphorus and simple sulfur; or lithium sulfide, diphosphorus pentasulfide, simple phosphorus and / or simple sulfur It can be used as a raw material.

For example, when the raw materials are lithium sulfide and diphosphorus pentasulfide, the mixing molar ratio is usually Li ₂ S: P ₂ S ₅ = 50: 50 to 80:20, preferably Li ₂ S: P ₂ S. ₅ = 60: 40 to 75:25. Particularly preferably, it is about Li ₂ S: P ₂ S ₅ = 70: 30 (molar ratio).

The sulfide-based solid electrolyte is preferably produced from (1) lithium sulfide and diphosphorus pentasulfide (2) lithium sulfide, simple phosphorus and simple sulfur or (3) lithium sulfide, diphosphorus pentasulfide, simple phosphorus and simple sulfur. be able to.
Specifically, after the mixture of the materials in any one of the above (1) to (3) is melt-reacted, it is cooled rapidly, or treated by a mechanical milling method (hereinafter sometimes referred to as MM method), thereby producing glass. A solid electrolyte is obtained. The obtained glassy solid electrolyte is further heat-treated to obtain a sulfide-based solid electrolyte that is a crystalline solid electrolyte.

  The average particle size of the sulfide-based solid electrolyte is preferably 0.01 to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 7 μm.

The positive electrode is made of a positive electrode mixture which is a mixture of the positive electrode active material of the present invention and a sulfide-based solid electrolyte.
The mixing ratio of the positive electrode active material of the present invention and the sulfide-based solid electrolyte in the positive electrode mixture is preferably positive electrode active material: electrolyte = 95: 5 to 50:50 (weight ratio).

The sulfide-based solid electrolyte contained in the electrolyte layer is the same as the sulfide-based solid electrolyte contained in the positive electrode described above.
The sulfide-based solid electrolyte contained in the electrolyte layer and the sulfide-based solid electrolyte contained in the positive electrode may be the same or different from each other, preferably the sulfide-based solid electrolyte contained in the electrolyte layer and the sulfide-based solid electrolyte contained in the positive electrode The solid electrolyte is the same.

  The all solid lithium battery of the present invention is composed of, for example, a positive electrode including the positive electrode active material of the present invention and a sulfide solid electrolyte, a negative electrode, and an electrolyte layer including a sulfide solid electrolyte sandwiched between the positive electrode and the negative electrode. The

FIG. 1 is a schematic cross-sectional view showing an embodiment of the all solid lithium battery of the present invention.
The all-solid-state lithium battery 1 includes a laminate in which a positive electrode 10, an electrolyte layer 20, and a negative electrode 30 are laminated in this order, a positive electrode current collector 40 and a negative electrode current collector 42 (the positive electrode current collector is a positive electrode current collector 40. The negative electrode current collector is sandwiched between the negative electrode current collectors 42).

  The positive electrode 10 and the electrolyte layer 20 are as described above. That is, the positive electrode 10 is made of a positive electrode mixture which is a mixture of the positive electrode active material of the present invention and a sulfide solid electrolyte, and the electrolyte layer 20 is made of a sulfide solid electrolyte.

The negative electrode 30 is not particularly limited as long as it can be used for a negative electrode of a battery.
The negative electrode 30 may be made of, for example, a negative electrode mixture that is a mixture of a negative electrode active material and a solid electrolyte, or may be a carbon negative electrode.

As said negative electrode active material, a commercially available negative electrode active material can be used without limitation, and a carbon material, Sn metal, Si metal, In metal, etc. can be used suitably.
Specific examples of the negative electrode active material include natural graphite, various graphites, metal powders such as Sn, Si, Al, Sb, Zn, and Bi, Sn ₅ Cu ₆ , Sn ₂ Co, Sn ₂ Fe, TiSi alloy, and NiSi alloy. Examples thereof include metal alloy powders such as alloys, metal oxide powders such as Si oxides, other amorphous alloys, and plating alloys.
The particle size of the negative electrode active material is not particularly limited, but the average particle size is preferably several μm to 80 μm.

As the solid electrolyte of the negative electrode mixture used for the negative electrode 30, for example, the sulfide-based solid electrolyte of the positive electrode 10 can be used.
The negative electrode mixture can be prepared by mixing the negative electrode active material and the solid electrolyte at a predetermined ratio.

Examples of the positive electrode current collector 40 and the negative electrode current collector 42 include metals such as stainless steel, gold, platinum, zinc, nickel, tin, aluminum, molybdenum, niobium, tantalum, tungsten, and titanium, and alloys thereof. It is done.
A current collector can be formed by forming the metal or alloy into a sheet, foil, net, punched metal, expanded metal, or the like.
In the present invention, it is preferable that the positive electrode current collector 40 is an aluminum foil and the negative electrode current collector 42 is an aluminum foil or a tin foil from the viewpoint of current collection, workability, and cost.

  The all solid lithium battery 1 is prepared, for example, by preparing a positive electrode mixture sheet in which the positive electrode 10 and the positive electrode current collector 40 are laminated, a negative electrode mixture sheet in which the negative electrode 30 and the negative electrode current collector 42 are laminated, and a solid electrolyte sheet. These can be manufactured by overlapping and pressing.

  The positive electrode mixture sheet and the negative electrode mixture sheet can be produced, for example, by forming the positive electrode 10 and the negative electrode 30 in a film shape on at least a part of the positive electrode current collector 40 and the negative electrode current collector 42, respectively. Examples of the film forming method include a blast method, an aerosol deposition method, a cold spray method, a sputtering method, a vapor phase growth method, and a thermal spraying method.

  In addition to the above method, the electrode mixture of the positive electrode 10 and the negative electrode 30 (positive electrode mixture and negative electrode mixture) is slurried, and the electrode mixture solution is applied onto the positive electrode current collector 40 and the negative electrode current collector 42, respectively. Alternatively, the positive electrode mixture sheet and the negative electrode mixture sheet can also be formed by laminating and compressing the electrode mixture of the positive electrode 10 and the negative electrode 30 on the positive electrode current collector 40 and the negative electrode current collector 42, respectively.

  The all-solid-state lithium battery 1 forms a laminate in which the positive electrode 10 and the electrolyte layer 20 are laminated in this order on the positive electrode current collector 40, and separately forms a laminate in which the negative electrode 30 is laminated on the negative electrode current collector 42. These two laminates can also be manufactured by superposing them so that the electrolyte layer 20 and the negative electrode 30 are in contact with each other.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example, unless the summary is exceeded.

Example 1
[Synthesis of positive electrode active material]
After dissolving metallic cobalt in 100 g nitric acid, it was diluted with pure water to 1650 ml. Subsequently, 820 ml of 4N sodium hydroxide solution was added and stirred, followed by filtration to obtain a hydroxide cake. The obtained cake was baked at 850 ° C. for 4 hours to obtain 137 g of cobalt oxide. Here, the lithium carbonate _(Li 2 CO ₃₎ was added and mixed cobalt oxide such that the Li / Co = 1.02, after 4 hours calcined at 700 ° C., for 5 hours main calcination at 1000 ° C., The target Li _X CoO ₂ (X = 1.02) was obtained.

[Preparation of sulfide-based solid electrolyte]
0.6508 g (0.01417 mol) of high purity lithium sulfide and 1.3492 g (0.00607 mol) of diphosphorus pentasulfide were mixed well, and the mixed powder was put into an alumina pot and completely sealed. The pot charged with the mixed powder was attached to a planetary ball mill, and milling was first performed at a low speed (85 rpm) for several minutes in order to sufficiently mix the starting materials. Thereafter, the rotational speed was gradually increased and mechanical milling was further performed at 370 rpm for 20 hours. It was confirmed by X-ray measurement that the obtained powder was vitrified, and this powder was heat treated at 300 ° C. for 2 hours to obtain a sulfide-based solid electrolyte.
When the ionic conductivity of the obtained sulfide-based solid electrolyte was measured by an AC impedance method (measurement frequency: 100 Hz to 15 MHz), it showed an ionic conductivity of 1.0 × 10 ⁻³ S / cm at room temperature.

[Preparation of positive electrode mixture]
Li _x CoO ₂ (X = 1.02), which was the synthesized positive electrode active material, and the prepared sulfide-based solid electrolyte were mixed so that the sulfide-based solid electrolyte would be 30 wt% to prepare a positive electrode mixture.

[Manufacture of lithium batteries]
50 mg of the prepared sulfide-based solid electrolyte was put into a plastic cylinder having a diameter of 10 mm, pressure-molded, and further prepared positive electrode mixture (positive electrode active material: Li _x CoO ₂ (X = 1.02)) 30 mg was added and pressure-molded again. An indium foil (thickness 0.1 mm, 9 mmφ) was introduced from the side opposite to the positive electrode mixture to form a three-layer structure of a positive electrode, a solid electrolyte layer, and a negative electrode, and a lithium battery was produced.
The produced lithium battery was charged to 3.9 V at 500 μA per cm ² , and then discharged at a discharge current density of 10 mA / cm ² to evaluate the discharge capacity and the discharge voltage. The results are shown in Table 1.

Example 2
In the synthesis of the positive electrode active material, was synthesized _{Li X CoO 2 (X = 1.04} ) was added lithium carbonate _(Li 2 CO ₃₎ so that the Li / Co = 1.04, the positive electrode active material A lithium battery was prepared and evaluated in the same manner as in Example 1 except that the positive electrode mixture was prepared. The results are shown in Table 1.

Example 3
In the synthesis of the positive electrode active material, lithium carbonate (Li ₂ CO ₃ ) was added so that Li / Co = 1.01 to synthesize Li _X CoO ₂ (X = 1.01). A lithium battery was prepared and evaluated in the same manner as in Example 1 except that the positive electrode mixture was prepared. The results are shown in Table 1.

Example 4
In the synthesis of the positive electrode active material, lithium carbonate (Li ₂ CO ₃ ) was added so that Li / Co = 1.03 to synthesize Li _X CoO ₂ (X = 1.03). A lithium battery was prepared and evaluated in the same manner as in Example 1 except that the positive electrode mixture was prepared. The results are shown in Table 1.

Example 5
[Preparation of negative electrode mixture]
Graphite (particle size: D50: 25 μm) and the sulfide-based solid electrolyte prepared in Example 1 were mixed so that graphite: sulfide-based solid electrolyte = 6: 4 (weight ratio) to prepare a negative electrode mixture. did.

[Production of lithium battery]
A lithium battery was prepared and evaluated in the same manner as in Example 1 except that 8.8 mg of the negative electrode mixture prepared instead of the indium foil was used and 14.4 mg of the positive electrode mixture of Example 1 was used. The results are shown in Table 1.

Example 6
A lithium battery was prepared and evaluated in the same manner as in Example 2 except that 8.8 mg of the negative electrode mixture of Example 5 was used instead of indium foil and 14.4 mg of the positive electrode mixture of Example 2 was used. The results are shown in Table 1.

Example 7
Preparation of Li _X (Ni _0.85 Co _0.15 ) O ₂ (X = 1.03) Particles After dissolving metallic nickel in 85 g and metallic cobalt in 15 g nitric acid, it was diluted with pure water to 1650 ml. Subsequently, 820 ml of 4N sodium hydroxide solution was added and stirred, followed by filtration to obtain a hydroxide cake. The obtained cake was dried at 100 ° C. for 10 hours to obtain 166 g of nickel cobalt composite hydroxide. Here, lithium hydroxide monohydrate (LiOH.H ₂ O) was added to and mixed with nickel-cobalt composite hydroxide so that Li / (Ni + Co) = 1.03, and calcined at 800 ° C., Li _X (Ni _0.85 Co _0.15 ) O ₂ (X = 1.03) was synthesized. The obtained Li _X (Ni _0.85 Co _0.15 ) O _{2 had} a particle size of 9.28 μm (D50) and a BET surface area of 0.24 m ² / g. A positive electrode mixture was prepared in the same manner as in Example 1 except that the positive electrode active material was used, and a lithium battery was produced.
The produced lithium battery was charged to 3.6 V at 500 μA per cm ² and then discharged at a discharge current density of 10 mA / cm ² to evaluate the discharge capacity and the discharge voltage. The results are shown in Table 1.

Example 8
Preparation of Li _X (Ni _0.82 Co _0.14 Al _0.04 ) O ₂ (X = 1.03) Particles After dissolving metallic nickel in 85 g and metallic cobalt in 15 g nitric acid, it was diluted with pure water to 1650 ml It was. Subsequently, 820 ml of 4N sodium hydroxide solution and 40 ml of 1 mol / l aluminum nitrate solution were added and stirred, followed by filtration to obtain a hydroxide cake. The obtained cake was dried at 100 ° C. for 10 hours to obtain 168 g of nickel cobalt composite hydroxide. Here, lithium hydroxide monohydrate (LiOH.H ₂ O) was added and mixed so that Li / (Ni + Co + Al) = 1.03, followed by firing at 800 ° C., and Li _X (Ni _0.82 Co _0.14 Al _0.04 ) O ₂ (X = 1.03) was synthesized. The resulting Li _{X (Ni} 0.85 _{Co 0.15)} particle size of the _{O 2} is 9.10μm (D50), BET surface area was 0.25 m ² / g. A positive electrode mixture was prepared in the same manner as in Example 9 except that the positive electrode active material was used, and a lithium battery was prepared and evaluated. The results are shown in Table 1.

Comparative Example 1
A lithium battery was prepared and evaluated in the same manner as in Example 1 except that a positive electrode mixture was prepared using Li _x CoO ₂ (X = 1.00) as the positive electrode active material. The results are shown in Table 1.

Comparative Example 2
In the synthesis of the positive electrode active material, lithium carbonate (Li ₂ CO ₃ ) was added so that Li / Co = 1.06 to synthesize Li _X CoO ₂ (X = 1.06). A lithium battery was prepared and evaluated in the same manner as in Example 1 except that the positive electrode mixture was prepared. The results are shown in Table 1.

  The all-solid-state lithium battery of the present invention can be used as a lithium battery for use in portable information terminals, portable electronic devices, small household power storage devices, motorcycles powered by motors, electric bicycles, hybrid electric vehicles, and the like.

DESCRIPTION OF SYMBOLS 1 All-solid-state lithium battery 10 Positive electrode 20 Electrolyte layer 30 Negative electrode 40 Positive electrode collector 42 Negative electrode collector

Claims (3)

An all-solid lithium battery comprising a positive electrode, an electrolyte layer and a negative electrode,
The all-solid-state lithium battery in which the said positive electrode contains the positive electrode active material and sulfide-type solid electrolyte which are represented by following formula (1), and the said electrolyte layer contains a sulfide-type solid electrolyte.
Li _a Ni _b Co _c Mn _{d Me} O _{f + σ} (1)
(Wherein, a is a number satisfying 1.01 ≦ a ≦ 1.05,
f is 2 or 4,
σ is −0.2 or more and 0.2 or less,
M is Mg, Ca, Y, rare earth element, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Cu, Ag, Zn, B, Al, Ga, C, Si, Sn, N , P, S, F, Cl.
When f is 2, b is a number satisfying 0 ≦ b ≦ 1, c is a number satisfying 0 ≦ c ≦ 1, d is a number satisfying 0 ≦ d ≦ 1, and e is 0 ≦ e It is a number that satisfies ≦ 0.5, and b + c + d + e = 1.
When f is 4, b is a number satisfying 0 ≦ b ≦ 2, c is a number satisfying 0 ≦ c ≦ 2, d is a number satisfying 0 ≦ d ≦ 2, and e is 0 ≦ e It is a number satisfying ≦ 1, and b + c + d + e = 2. ) The positive electrode active material is Li _a CoO _{2 + σ} , Li _a Ni _{0.8 ± 0.1} Co _{0.15 ± 0.1} Al _{0.05 ± 0.05} O _{2 + σ} , Li _a Ni _{0.8 ± 0.1} Co _{0.2 ± 0.1} O _{2 + σ} , Li _a NiO _{2 + σ} , Li _a Mn ₂ O ₄ , Li _a Mn _0.5 Ni _0.5 O ₂ , Li _a Mn _1.5 Ni _0.5 O ₄ , or Li all-solid lithium battery according to claim 1 which is _{a Mn 1/3 Ni 1/3 Co 1/3 O} 2.   The all-solid-state lithium battery according to claim 1, wherein a is a number satisfying 1.01 ≦ a ≦ 1.04.

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