JPH0765836A - Manufacture of positive electrode active material for high polymer solid electrolyte lighium battery - Google Patents

Abstract

PURPOSE:To manufacture a positive electrode active material for a high polymer solid electrolyte lithium battery which is used to form a positive electrode active material layer containing LixV2O5.nH2O with an X value in a preset range. CONSTITUTION:Mixed slurry S is manufactured by mixing vanadium pentoxide xerogel powder, lithium ion conductive high polymer solid electrolyte solution and conductive assistant. Electrolytic slurry containing lithium vanadium pentoxide xerogel is manufactured by electrolyzing the mixed slurry S put in an electrolyzer which has a stirring member 5 inside to constitute a cathode and an anode-side electrolyzing member (lithium metal) 3 arranged in an anode 2 while operating the stirring member 5. After solvent is volatilized and removed from the electrolytic slurry taken out of the electrolyzer, the electrolytic slurry is rolled into a sheet with roller press to form a positive electrode active material sheet. A prescribed shape of positive electrode active material for a high polymer solid electrolyte lithium battery is obtained from the positive electrode active material sheet.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a positive electrode active material for a polymer solid electrolyte lithium battery.

[0002]

_2. Description of the Related Art A positive electrode active material layer made of a positive electrode active material such as MnO ₂ , V ₂ O ₅ .nH ₂ O and a negative electrode active material layer made of metallic lithium are laminated with a polymer solid electrolyte layer interposed therebetween. A polymer solid electrolyte lithium battery having a different structure is known. In this type of battery, when the lithium-containing positive electrode active material (discharge product) in which metallic lithium of the negative electrode active material is compounded is previously contained in the positive electrode active material layer before the battery is first discharged, It is known that the charge and discharge cycle characteristics of can be improved. Therefore, various methods of incorporating a lithium-containing positive electrode active material in which metallic lithium is composited into the positive electrode active material layer have been conventionally studied. Among the above-mentioned positive electrode active material materials, in the case of oxides of transition metals such as MnO ₂ , when chemically synthesized by mixing with a lithium salt and heating at a high temperature, these oxides are thermally decomposed to form LiMnO 2. ₂
Since the lithium-containing positive electrode active material shown by is obtained, the lithium-containing positive electrode active material can be easily obtained.

[0003]

However, from vanadium pentoxide xerogel (V ₂ O ₅ .nH ₂ O) to Li
When such a chemical synthesis method is used for producing a lithium-containing positive electrode active material represented by xV ₂ O ₅ .nH ₂ O, V ₂ O ₅ .nH ₂ O crystallizes by heating,
V ₂ O ₅ · nH ₂ O cannot be combined with Li,
LixV ₂ O ₅ .nH ₂ O cannot be obtained. Further, a lithium salt such as t-butyllithium or lithium hydroxide was added to an aqueous solution of amorphous vanadium pentoxide (V ₂ O ₅ ), which was dissolved and dried to obtain vanadium pentoxide xerogel (V ₂ O _5). .NH ₂ O) was also considered, but since an aqueous solution of amorphous vanadium pentoxide (V ₂ O ₅ ) gels, LixV ₂ O ₅ can be formed by such a method.
-It was not possible to obtain nH ₂ O. Also, LixV
_{Since 2} O ₅ .nH ₂ O is a discharge product, it is possible to cause the lithium-containing positive electrode active material to be included in the positive electrode active material layer by performing over-discharge before first using the battery. However, if the battery is simply over-discharged, the entire positive electrode active material layer will have a lithium-containing positive electrode active material (L
ixV ₂ O ₅ .nH ₂ O) cannot be dispersed substantially uniformly, and the charge / discharge cycle characteristics of the battery cannot be sufficiently enhanced.

An object of the present invention is to positive electrode active material for polymer solid electrolyte lithium battery which can be used to form a positive electrode active material layer containing LixV ₂ O ₅ .nH ₂ O having an X value in a predetermined range. It is to provide a method for producing a substance.

[0005]

The invention according to claim 1 is directed to a method for producing a positive electrode active material for a polymer solid electrolyte lithium battery. In the present invention, first, a solution in which a solid polymer electrolyte is dissolved in a solvent and vanadium pentoxide xerogel powder are provided in an electrolytic cell in which a stirring member is provided inside and metallic lithium is arranged in the anode, and the stirring member is operated. Electrolysis is performed to prepare an electrolytic slurry containing lithium-containing vanadium pentoxide xerogel represented by LixV ₂ O ₅ .nH ₂ O. Then, the solvent is volatilized and removed from the electrolytic slurry taken out of the electrolytic cell to produce a positive electrode active material for a polymer solid electrolyte lithium battery. Incidentally, the solution obtained by dissolving the solid polymer electrolyte in a solvent and the vanadium pentoxide xerogel powder may be placed in an electrolytic cell in a mixed slurry state in which both are mixed,
Both may be placed separately in the electrolytic cell.

According to the invention of claim 2, LixV ₂ O ₅ · n
Electrolysis is performed in the electrolytic cell so that the value of x of H ₂ O is 0.05 <x <3.0. The value of x can be easily changed by adjusting the amount of electricity applied during electrolysis.

In the invention of claim 3, the stirring member is a cathode.

The invention of claim 4 is directed to a method for producing a positive electrode active material for a polymer solid electrolyte lithium battery. In the present invention, first, a vanadium pentoxide xerogel film is pulverized to prepare a vanadium pentoxide xerogel powder, and a lithium salt is dissolved in a solution of a polyphosphazene derivative dissolved in a solvent to obtain a lithium ion conductive polymer solid electrolyte solution. make. Next, the vanadium pentoxide xerogel powder, the lithium ion conductive polymer solid electrolyte solution, and the conduction aid are mixed to form a mixed slurry. Next, an agitating member is provided inside, the agitating member is used as a cathode, and the mixed slurry is put into an electrolytic cell in which metallic lithium is placed in the anode, and electrolysis is performed while the agitating member is operated to perform electrolysis slurry containing lithium-containing vanadium pentoxide xerogel. make. Next, a solvent is volatilized and removed from the electrolytic slurry taken out of the electrolytic cell and rolled into a sheet by a roller press to make a positive electrode active material sheet, and the positive electrode active material sheet has a predetermined shape for a positive electrode for a polymer solid electrolyte lithium battery. Manufacture active material.

[0009]

According to the first aspect of the present invention, vanadium pentoxide xerogel (V ₂ O ₅ .nH ₂ O) is converted to LixV ₂ O by electrolysis.
_This is a method for producing a lithium-containing positive electrode active material represented by ₅ · nH ₂ O. In the present invention, the solid polymer electrolyte is used as an electrolyte for electrolysis, and a mixture of vanadium pentoxide xerogel powder and a solution of the polymer solid electrolyte dissolved in a solvent is subjected to an electric current treatment to obtain LixV ₂ O ₅・ NH ₂
A lithium-containing positive electrode active material represented by O can be easily prepared. Moreover, according to the present invention, since the vanadium pentoxide xerogel powder in the mixture is electrolyzed while stirring the mixture, the lithium-containing positive electrode active material (LixV ₂ O) having an X value within a predetermined range in the entire positive electrode active material layer is electrolyzed. ₅ · nH ₂ O) can be dispersed substantially evenly.

In the electrolysis for producing the electrolytic slurry, the value x of LixV ₂ O ₅ .nH ₂ O is 0.05 as in the invention of claim 2.
It is preferable to carry out so that <x <3.0. When a positive electrode active material containing LixV ₂ O ₅ .nH ₂ O having a value of x of 0.05 or less is used in a battery in which a metallic lithium (negative electrode active material) layer is arranged on the negative electrode side and which does not require initial charging, discharge occurs. There arises a problem that the capacity retention rate of the capacity (the ratio of the discharge capacity after the second cycle to the discharge capacity at the first time) decreases. The reason for this is not clear, but a battery containing a lithium-containing positive electrode active material (LixV ₂ O ₅ .nH ₂ O) in the positive electrode active material layer has a value of x of 0.05 or less even after charging. This is because the battery cannot be charged until that time. Further, when the value of x is 3.0 or more, there is a problem that the positive electrode active material is difficult to return to the charge product.

When the stirring member is configured as a cathode as in the third aspect of the invention, the device of the battery case for electrolysis can be simplified and the electrolysis efficiency (Coulomb efficiency) can be improved.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A manufacturing method of an embodiment of the present invention will be described in detail below with reference to the drawings. First, vanadium pentoxide xerogel powder was prepared as follows. First, an aqueous solution containing 3% by weight of amorphous vanadium pentoxide is applied on a substrate such as a stainless steel plate or a tetrafluoroethylene resin plate and then dried to form a vanadium pentoxide xerogel (V ₂ O ₅ · nH ₂ O) film. did. The value of n of V ₂ O ₅ · nH ₂ O is 0.1 <n
It is preferable to form V ₂ O ₅ .nH ₂ O so as to be in the range of <1.6. When the value of n is 0.1 or less, there is a problem that vanadium pentoxide is likely to crystallize. When the value of n is 1.6 or more, the negative electrode active material (lithium)
Reacts with an excess of bound water, so that there is a problem that the battery performance deteriorates. Next, the vanadium pentoxide xerogel film was peeled off from the substrate and crushed, and then 120 ° C, 10 ^-2
It was dried under reduced pressure at atmospheric pressure for 16 hours to prepare vanadium pentoxide xerogel powder having an average particle size of 10 μm.

Next, methoxyoligoethyleneoxypolyphosphazene (MEP), which is one of the polyphosphazene derivatives, and 8% by weight of LiClO _{4 based on the} MEP.
A lithium salt consisting of 1,2-dimethoxyethane (D
13% by weight was dissolved in a solvent consisting of ME) to prepare a solution for a lithium ion conductive polymer solid electrolyte. Incidentally, ME
The amount of LiClO ₄ with respect to P is preferably 3 to 18% by weight, and the proportion of the mixture of MEP and LiClO ₄ dissolved in DME is preferably 5 to 20% by weight.

Next, the above-mentioned vanadium pentoxide xerogel powder, the solution for polymer solid electrolyte and acetylene black (A
The conductive auxiliary material consisting of B) was mixed at a weight ratio of 5: 3: 2 to prepare a mixed slurry. The acetylene black used was dried under reduced pressure at 150 ° C. and 10 ⁻² atm for 48 hours. Then, the mixed slurry is put into the electrolytic cell shown in the schematic sectional view of FIG. 1, and the vanadium pentoxide xerogel (V ₂ O ₅ · n) in the mixed slurry S is stirred while stirring the mixed slurry.
H ₂ O) powder was converted to lithium-containing vanadium oxide xerogel (LixV ₂ O ₅ .nH ₂ O) by the following reaction formula to prepare an electrolytic slurry containing lithium-containing vanadium pentoxide xerogel. V ₂ O ₅ · nH ₂ O + xLi ⁺ + xe ⁻ → LixV ₂ O
₅ · nH ₂ O Here, the structure of the electrolytic cell shown in FIG. 1 will be described.
In the figure, 1 is an electrolysis container, 2 is an anode, 3 is an anode side electrolysis member, 4 is a separator, 5 is a stirring member constituting a cathode, 6 is a power source, 7 Is a lid for the electrolytic container. The electrolytic container 1 is made of glass and has a cylindrical shape with a diameter of 50 mm and a height of 50 mm. The anode 2 has a structure in which a terminal portion 2b is connected to a net portion 2a made of stainless steel. The mesh portion 2a has a cylindrical shape, and faces the inner wall surface 1a of the electrolytic container 1 with a predetermined gap. The terminal portion 2b is supported by the lid portion 7, and the end portion thereof is connected to the positive electrode output terminal of the power source 6. The anode electrolytic member 3 is made of 500 g of metallic lithium, and is pressed against the entire inner wall portion 2c of the mesh portion 2a of the anode 2. The separator 4 is formed of polypropylene non-woven fabric, and divides the inside of the electrolytic container 1 into an anode region 1b and a cathode region 1c. The anode region 1b is filled with a solution Y for lithium ion conductive polymer solid electrolyte having the same composition as that used for preparing the above-mentioned electrolytic slurry, and the cathode region 1
The mixed slurry S is filled in c. The side surface 4a of the separator 4 on the positive electrode region 1b side is joined to the anode side electrolytic member 3 and is supported by the anode side electrolytic member 3. The stirring member 5 has a structure in which four stirring blades 5b are connected to a rotating shaft 5a at equal angular intervals. The rotating shaft 5a is formed of a stainless tube, and one end thereof is connected to the negative output terminal of the power supply 6. The rotating shaft 5a is rotatably supported by the electrolytic vessel lid 7 via a bearing (not shown), and is rotationally driven by a motor (not shown). The stirring blade 5b is configured by attaching a stainless steel net to a stainless steel frame fixed to the rotating shaft 5a. The mesh shape and size of the mesh are determined so that the mixed slurry S in the negative electrode region 1c can be evenly stirred. Like the electrolytic container 1, the electrolytic container lid 7 is made of glass.

In this embodiment, the amount of the vanadium pentoxide xerogel powder in the mixed slurry S is 5 g, and the rotating shaft 5a
Rotating at 20 r / m, the electrolysis current is set to 10 mA, the cut voltage is set to 2.5 V, current is applied until the electrolysis current reaches the cut voltage, and then constant voltage is applied at 2.5 V (30 ° C.) to perform electrolysis. Electrolysis was performed until the coulomb amount of the coulometer installed in the external circuit reached 2650 coulomb. When electrolysis is performed until the coulomb amount becomes 2650 coulomb, Li
The average value of x of xV ₂ O ₅ .nH ₂ O is 1.0.

Next, after taking out the electrolytic slurry from the electrolytic cell, the electrolytic slurry was left in an atmosphere of 40 ° C. for 24 hours to volatilize and remove the solvent (DME) from the electrolytic slurry.
Then, the electrolytic slurry from which the solvent is volatilized and removed is rolled into a sheet by a roller press to form a positive electrode active material sheet,
This positive electrode active material sheet has a thickness of 1.18 mm × 35 mm × 35
It was cut into a size of mm to complete a positive electrode active material for a polymer solid electrolyte lithium battery having a predetermined shape. The lithium-containing vanadium pentoxide xerogel (LixV ₂
O ₅ · nH ₂ O) was 0.1 g.

Next, a flat type solid polymer electrolyte lithium battery having a cross section as shown in FIG. 2 was manufactured as follows using the positive electrode active material manufactured by the method of this example, and the cycle of this battery was manufactured. The life characteristics were investigated. First, the thickness is 20 μm
One surface 11 of the positive electrode current collector 11 made of nickel foil
The positive electrode active material produced by the method of this example was attached to the central portion of a to form a positive electrode active material layer 12 made of vanadium pentoxide xerogel (V ₂ O ₅ .nH ₂ O) having a thickness of 1.18 mm.

Next, a lithium holder layer (negative electrode active material holder layer) 13 was prepared as follows. First, the lithium ion conductive polymer solid electrolyte used in producing the above-mentioned positive electrode active material so that the weight ratio of natural graphite and methoxyoligoethyleneoxypolyphosphazene (MEP) is 3: 7. Was thoroughly kneaded with the working solution. Then, this was left in an atmosphere of 40 ° C. for 24 hours to volatilize and remove the solvent (DME) to prepare a negative electrode active material holder material. Next, this negative electrode active material holding material is rolled into a sheet by a roller press to form a negative electrode active material holding sheet.
The negative electrode active material holder having a predetermined shape was completed by cutting into a size of mm × 35 mm × 35 mm. Then, a negative electrode active material holder was attached to the central portion of one surface 14a of the negative electrode current collector 14 made of a stainless steel foil having a thickness of 20 μm to form a negative electrode active material holder layer 13 having a thickness of 0.1 mm.

Next, the hot melt 15 is placed on the outer peripheral end portion 11b of the positive electrode current collector 11, and then the positive electrode active material layer 12 is entirely covered so that lithium ion conduction is performed on the positive electrode active material layer 12. The solution for the organic polymer solid electrolyte was applied. Then, the lithium ion conductive polymer solid electrolyte solution was dried. Further, the solution for lithium ion conductive polymer solid electrolyte was applied on the negative electrode active material holder layer 13, and then the solution for lithium ion conductive polymer solid electrolyte was dried. Then, the positive electrode current collector 11 and the negative electrode current collector 14 were laminated so that the positive electrode active material layer 12 and the negative electrode active material holder layer 13 faced each other. When laminated in this way, the dry state lithium ion conductive polymer solid electrolyte solution applied to both layers is bonded between the positive electrode active material layer 12 and the negative electrode active material holder layer 13 to have a thickness of 100 μm. The polymer solid electrolyte layer 16 is formed. Next, by heating, the hot melt 15 is applied to the outer peripheral end portions 11b and 1 of the current collectors 11 and 14.
4b was completely connected to complete a solid polymer electrolyte lithium battery. As described above, a lithium-containing vanadium pentoxide xerogel (LixV ₂ O ₅ .nH) containing a positive electrode active material layer of a polymer solid electrolyte lithium battery in which the lithium ion carrier (negative electrode active material carrier) doped with lithium ions is arranged on the negative electrode side.
_If it is composed of ₂ O), it is not necessary to dispose the negative electrode active material in the negative electrode active material holder, and the manufacture of the battery is simplified.

Next, this battery was set to have an electrolysis current of 0.5 mA and a cut voltage of 2.5 V, energized until the electrolysis current reached the cut voltage, and then subjected to constant voltage charging at 4.0 V and after initial charging. The battery was repeatedly charged and discharged to examine the charge and discharge cycle characteristics of the battery. The charging / discharging was performed under the following conditions. Discharge: 0.5 mA, final voltage: 2.0 V (25 ° C) Charge: 0.5 mA, final voltage: 4.0 V (25 ° C),
Combined use with 4.0V constant voltage charging Fig. 3 shows the measurement results of charge / discharge cycle characteristics. From this figure, it can be seen that by using the positive electrode active material manufactured by the method of this example, a battery capable of maintaining a relatively high battery capacity of 13 mAh even after exceeding 200 cycles can be obtained.

Next, a battery A using two kinds of positive electrode active materials,
B was manufactured, and the initial discharge capacity retention rate (the ratio of the discharge capacity at each cycle to the discharge capacity of the initial discharge) for the charge / discharge cycle of each battery was examined. The positive electrode active material of the battery A is a positive electrode active material manufactured by the method of another embodiment of the present invention, and electrolysis is performed until the average value of x of LixV ₂ O ₅ .nH ₂ O becomes 0.1, and Was manufactured in the same manner as in the above-mentioned example. The positive electrode active material of the battery B is V ₂ O ₅ · nH ₂
It is a positive electrode active material represented by O that does not contain Li. In both batteries A and B, 25 mg was used instead of the negative electrode active material holder layer.
A negative electrode active material layer is formed from the metallic lithium, and has the same structure as the battery shown in FIG. 2 except for the negative electrode active material holder layer and the positive electrode active material layer. And the batteries A and B
The charging / discharging under the same condition as the charging / discharging cycle characteristic test shown in FIG. FIG. 4 shows the measurement result. As shown in the figure, the battery A using the positive electrode active material manufactured by the method of the other embodiment of the present invention has a high initial discharge capacity retention rate even after 40 charge / discharge cycles (approximately 100).
%), The battery B using a positive electrode active material containing no Li has a low initial discharge capacity retention rate (approximately 90%).
%) Is understood. This is because in the battery A, Li taken into the positive electrode active material by the first discharge is desorbed by the first charge performed next time, so that the capacity of the second discharge can be maintained at a high level. In the battery B using the positive electrode active material not containing Li, the Li taken into the positive electrode active material by the first discharge is the Li taken in even when the battery is charged by the first charge performed next.
This is because 10% of the residual amount remains in the positive electrode active material and the capacity of the second discharge is reduced by 10%.

In this embodiment, the stirring member is composed of the cathode, but the present invention is not limited to this, and it goes without saying that the stirring member and the cathode may be separately structured.

[0023]

According to the first aspect of the present invention, vanadium pentoxide xerogel (V ₂ O ₅ .nH ₂ O) is converted to Lix by electrolysis.
This is a method for producing a lithium-containing positive electrode active material represented by V ₂ O ₅ .nH ₂ O. In the present invention, by using the polymer solid electrolyte in the mixed slurry as an electrolyte for electrolysis, by conducting an electric current treatment on a mixture of a solution of vanadium pentoxide xerogel powder and a polymer solid electrolyte dissolved in a solvent. A lithium-containing positive electrode active material represented by LixV ₂ O ₅ .nH ₂ O can be easily prepared. Moreover, according to the present invention, since the vanadium pentoxide xerogel powder in the mixture is electrolyzed while stirring the mixture, the lithium-containing positive electrode active material (Li-containing positive electrode active material (Li
xV ₂ O ₅ .nH ₂ O) can be dispersed substantially evenly.

According to the invention of claim 2, when used in a battery in which a metallic lithium (negative electrode active material) layer is arranged on the negative electrode side and which does not require initial charging, the capacity retention ratio of discharge capacity (2 to the initial discharge capacity is 2 The ratio of the discharge capacity after the second cycle can be maintained high, and the problem that the positive electrode active material is difficult to return to the charge product can be solved.

According to the third aspect of the present invention, since the stirring member is configured as a cathode, it is possible to simplify the device of the battery cell for electrolysis and to improve the electrolysis efficiency (Coulomb efficiency).

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an electrolytic cell used in the manufacturing method of this embodiment.

FIG. 2 is a cross-sectional view of a battery using the positive electrode active material manufactured by the method of this example.

FIG. 3 is a diagram showing charge / discharge cycle characteristics of a battery using the positive electrode active material manufactured by the method of this example.

FIG. 4 is a diagram showing the initial discharge capacity retention rate with respect to the charge / discharge cycle of the battery used in the test.

[Explanation of symbols]

 2 Anode 3 Anode side electrolytic member (metal lithium) 5 Cathode (stirring member)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hayakawa et al. ▲ Ku ▼ Beauty 2-1, 1-1 Nishinishinjuku, Shinjuku-ku, Tokyo Shin-Kindo Electric Co., Ltd. (72) Inventor Akio Komaki Nishishinjuku, Shinjuku-ku, Tokyo 2-1-1 No. 1 Shinshin Todo Electric Co., Ltd. (72) Inventor Akika Inubushi 463, Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd., Tokushima Research Institute (72) Inventor Nakafumi, Weibun Tokushima, Tokushima Prefecture 463 Kagasuno, Ichikawauchi-machi, Tokushima Research Institute, Otsuka Chemical Co., Ltd. (72) Inventor, Michio Sasaoka, 463, Kagasuno, Kawauchi-machi, Tokushima, Tokushima Prefecture, Tokushima Research Institute, Otsuka Chemical Co., Ltd.

Claims (4)

[Claims] 1. A solution in which a solid polymer electrolyte is dissolved in a solvent and vanadium pentoxide xerogel powder are placed in an electrolytic cell equipped with a stirring member inside and lithium metal is placed in the anode, and the stirring member is operated. While carrying out electrolysis, L
ixV2O5.nH2O, an electrolytic slurry containing lithium-containing vanadium pentoxide xerogel represented by ixV2O5.nH2O is prepared, and the solvent is volatilized and removed from the electrolytic slurry taken out from the electrolytic cell to produce a positive electrode active material for a polymer electrolyte lithium battery. A method for producing a positive electrode active material for a polymer solid electrolyte lithium battery, comprising: 2. The x of the LixV2 O5 .nH2 O
The method for producing a positive electrode active material for a polymer solid electrolyte lithium battery according to claim 1, wherein electrolysis is performed in the electrolytic cell such that the value of is 0.05 <x <3.0. 3. The method for producing a positive electrode active material for a polymer solid electrolyte lithium battery according to claim 1, wherein the stirring member is a cathode. 4. A vanadium pentoxide xerogel film is crushed to produce a vanadium pentoxide xerogel powder, and a lithium salt is dissolved in a solution of a polyphosphazene derivative in a solvent to obtain a lithium ion conductive polymer solid electrolyte solution. A mixed slurry is prepared by mixing the vanadium pentoxide xerogel powder, the lithium ion conductive polymer solid electrolyte solution and a conductive auxiliary material, and a stirring member is provided inside, and the stirring member is used as a cathode and a metal is used as an anode. Put the mixed slurry in an electrolytic cell in which lithium is placed to perform electrolysis while operating the stirring member to make an electrolytic slurry containing lithium-containing vanadium pentoxide xerogel, and remove the solvent from the electrolytic slurry taken out from the electrolytic cell. The material that has been volatilized and removed is rolled into a sheet by a roller press, and the positive electrode active material Making a chromatography bets, the positive electrode active material manufacturing method of positive active material for solid polymer electrolyte lithium battery, characterized in that the sheet to produce a positive active material for solid polymer electrolyte lithium battery having a predetermined shape from.