JP2018120841A - Method for manufacturing electrode member for all-solid battery - Google Patents
Method for manufacturing electrode member for all-solid battery Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
本開示は、全固体電池用電極部材の製造方法に関する。 The present disclosure relates to a method for manufacturing an electrode member for an all-solid battery.
近年におけるパソコン、ビデオカメラおよび携帯電話等の情報関連機器や通信機器等の急速な普及に伴い、その電源として利用される電池の開発が重要視されている。また、自動車産業界等においても、電気自動車用あるいはハイブリッド自動車用の高出力かつ高容量の電池の開発が進められている。
リチウムイオン全固体電池は、リチウムイオンの移動を伴う電池反応を利用するためエネルギー密度が高いという点、また、正極と負極の間に介在する電解質として、有機溶媒を含む電解液に替えて固体電解質を用いるという点で注目されている。
With the rapid spread of information-related equipment and communication equipment such as personal computers, video cameras, and mobile phones in recent years, development of batteries that are used as power sources has been regarded as important. Also in the automobile industry and the like, development of high-power and high-capacity batteries for electric vehicles or hybrid vehicles is being promoted.
Lithium-ion all-solid-state batteries have a high energy density because they use a battery reaction involving the movement of lithium ions, and the electrolyte interposed between the positive electrode and the negative electrode is replaced with an electrolyte containing an organic solvent as a solid electrolyte. It is attracting attention in terms of using.
Ｓｉ系材料からなる活物質は、体積当たりの理論容量が大きいことから、Ｓｉ系材料を負極に用いたリチウムイオン全固体電池が提案されている。
特許文献１には、固体電解質層の一方の表面にＳｉ含有活物質の粉末と固体電解質材料の粉末を含む負極用合材を添加し、プレスすることにより前駆層を形成し、固体電解質層の反対側の表面に対極層を形成した電池部材を準備し、当該電池部材に対し、積層方向に１５０ｋｇｆ／ｃｍ２以上の拘束圧を印加した状態で、充放電処理を複数回行うことで、Ｓｉ含有活物質層を製造する方法が開示されている。
Since an active material made of a Si-based material has a large theoretical capacity per volume, a lithium ion all-solid battery using the Si-based material as a negative electrode has been proposed.
In Patent Document 1, a negative electrode mixture containing a powder of an Si-containing active material and a powder of a solid electrolyte material is added to one surface of the solid electrolyte layer, and a precursor layer is formed by pressing. By preparing a battery member having a counter electrode layer formed on the surface on the opposite side and applying a constraint pressure of 150 kgf / cm 2 or more in the stacking direction to the battery member, the charge / discharge treatment is performed a plurality of times to obtain Si A method for producing a contained active material layer is disclosed.
また、特許文献２には、無機固体電解質と、式（１）：ＳｉｘＭ（１−ｘ）で表される活物質と、粒子ポリマーを含む固体電解質組成物を集電体上に塗布し、乾燥することにより、負極活物質層を形成することが記載されている。 In Patent Document 2, a solid electrolyte composition containing an inorganic solid electrolyte, an active material represented by formula (1): Si x M (1-x) , and a particle polymer is applied to a current collector. And forming a negative electrode active material layer by drying.
特許文献１及び２のリチウムイオン全固体電池においては、負極中にＳｉ系材料と共に結着材や固体電解質を含有している。
一方、全固体電池の電極中にＳｉ系材料と共に結着材や固体電解質を共存させない場合には、Ｓｉ系材料の粒子相互の接触性が不十分となり、充分な電池性能が得られにくくなる。
そのため、全固体電池の電極にＳｉ系材料を用いる場合には、Ｓｉ系材料の粒子相互の接触性を向上させるために電極内に結着材や固体電解質を含有させる必要がある。
しかし、全固体電池の電極中にＳｉ系材料と共に結着材や固体電解質を共存させる場合には、Ｓｉ系材料そのものの体積当たり理論容量は大きいにもかかわらず、電極中でのＳｉ系材料の含有量が少なくなるため、電池全体としてのエネルギー密度が低くなるという問題がある。
本開示は、上記実情に鑑み、活物質としてＳｉ系材料を含む負極を有し、エネルギー密度が高い全固体電池用の電極部材の製造方法を提供することを目的とする。
In the lithium ion all solid state batteries of Patent Documents 1 and 2, the negative electrode contains a binder and a solid electrolyte together with the Si-based material.
On the other hand, when the binder and the solid electrolyte are not allowed to coexist with the Si-based material in the electrode of the all-solid-state battery, the contact property between the particles of the Si-based material becomes insufficient, and it becomes difficult to obtain sufficient battery performance.
Therefore, in the case of using a Si-based material for the electrode of the all-solid-state battery, it is necessary to include a binder or a solid electrolyte in the electrode in order to improve the contact property between the particles of the Si-based material.
However, when a binder and a solid electrolyte coexist with the Si-based material in the electrode of the all-solid-state battery, the theoretical capacity per volume of the Si-based material itself is large, but the Si-based material in the electrode Since the content is reduced, there is a problem that the energy density of the entire battery is lowered.
This indication aims at providing the manufacturing method of the electrode member for all-solid-state batteries which has a negative electrode containing Si type material as an active material, and has a high energy density in view of the said situation.
本開示は、正極と、負極と、当該正極及び当該負極の間に配置される固体電解質層と、を備える全固体電池用の電極部材の製造方法であって、
Ｌｉを含有する正極活物質を含む正極材料部、負極活物質としてＳｉ単体粉末を含み且つ結着材及び固体電解質を含まない負極材料部、並びに、前記正極材料部と前記負極材料部の間に配置された固体電解質材料部を備えた１次組立体を準備する準備工程、並びに、
前記１次組立体に、前記正極材料部、前記固体電解質材料部及び前記負極材料部の配列方向に１００ＭＰａ以上の拘束圧を印加した状態で、前記正極材料部側から前記固体電解質材料部を経由して前記負極材料部側に至る方向へ、負極材料部に含まれるＳｉ単体粉末１ｇ当たり９１０ｍＡｈ以上の電気量となるように通電し、前記負極材料部にＬｉイオンを挿入する通電工程を有する、全固体電池用電極部材の製造方法を提供する。
The present disclosure is a method for producing an electrode member for an all-solid battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode,
A positive electrode material portion containing a positive electrode active material containing Li, a negative electrode material portion containing Si simple powder as a negative electrode active material and not containing a binder and a solid electrolyte, and between the positive electrode material portion and the negative electrode material portion A preparatory step of preparing a primary assembly with a disposed solid electrolyte material portion, and
The primary assembly is passed through the solid electrolyte material portion from the positive electrode material portion side in a state where a binding pressure of 100 MPa or more is applied to the primary assembly in the arrangement direction of the positive electrode material portion, the solid electrolyte material portion, and the negative electrode material portion. Then, in the direction to reach the negative electrode material part side, it has an energization step of energizing so that the amount of electricity is 910 mAh or more per 1 g of Si simple substance powder contained in the negative electrode material part, and inserting Li ions into the negative electrode material part. A method for producing an electrode member for an all-solid-state battery is provided.
上記製造方法によれば、活物質としてＳｉ系材料を含む負極を有し、エネルギー密度が高い全固体電池用の電極部材の製造方法が提供される。 According to the said manufacturing method, the manufacturing method of the electrode member for all-solid-state batteries which has a negative electrode containing Si type material as an active material, and has a high energy density is provided.
本開示は、正極と、負極と、当該正極及び当該負極の間に配置される固体電解質層と、を備える全固体電池用の電極部材の製造方法であって、
Ｌｉを含有する正極活物質を含む正極材料部、負極活物質としてＳｉ単体粉末を含み且つ結着材及び固体電解質を含まない負極材料部、並びに、前記正極材料部と前記負極材料部の間に配置された固体電解質材料部を備えた１次組立体を準備する準備工程、並びに、
前記１次組立体に、前記正極材料部、前記固体電解質材料部及び前記負極材料部の配列方向に１００ＭＰａ以上の拘束圧を印加した状態で、前記正極材料部側から前記固体電解質材料部を経由して前記負極材料部側に至る方向へ、負極材料部に含まれるＳｉ単体粉末１ｇ当たり９１０ｍＡｈ以上の電気量となるように通電し、前記負極材料部にＬｉイオンを挿入する通電工程を有する、全固体電池用電極部材の製造方法を提供する。
The present disclosure is a method for producing an electrode member for an all-solid battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode,
A positive electrode material portion containing a positive electrode active material containing Li, a negative electrode material portion containing Si simple powder as a negative electrode active material and not containing a binder and a solid electrolyte, and between the positive electrode material portion and the negative electrode material portion A preparatory step of preparing a primary assembly with a disposed solid electrolyte material portion, and
The primary assembly is passed through the solid electrolyte material portion from the positive electrode material portion side in a state where a binding pressure of 100 MPa or more is applied to the primary assembly in the arrangement direction of the positive electrode material portion, the solid electrolyte material portion, and the negative electrode material portion. Then, in the direction to reach the negative electrode material part side, it has an energization step of energizing so that the amount of electricity is 910 mAh or more per 1 g of Si simple substance powder contained in the negative electrode material part, and inserting Li ions into the negative electrode material part. A method for producing an electrode member for an all-solid-state battery is provided.
上記製造方法には、次の一態様が含まれる。
正極と、負極と、当該正極及び当該負極の間に配置される固体電解質層と、を備える全固体電池用の電極部材の製造方法であって、
Ｌｉを含有する正極活物質を含む正極材料層、負極活物質としてＳｉ単体粉末を含み且つ結着材及び固体電解質を含まない負極材料層、並びに、前記正極材料層と前記負極材料層の間に配置された固体電解質材料層を備えた１次組立体を準備する準備工程、並びに、
前記１次組立体に、前記正極材料層、前記固体電解質材料層及び前記負極材料層の積層方向に１００ＭＰａ以上の拘束圧を印加した状態で、前記正極材料層側から前記固体電解質材料層を経由して前記負極材料層側に至る方向へ、負極材料層に含まれるＳｉ単体粉末１ｇ当たり、９１０ｍＡｈ以上の電気量となるように通電し、前記負極材料層にＬｉイオンを挿入する通電工程を有する、全固体電池用電極部材の製造方法を提供する。
The manufacturing method includes the following aspect.
A method for producing an electrode member for an all-solid battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode,
A positive electrode material layer containing a positive electrode active material containing Li, a negative electrode material layer containing Si simple powder as a negative electrode active material and not containing a binder and a solid electrolyte, and between the positive electrode material layer and the negative electrode material layer A preparatory step of preparing a primary assembly with a disposed solid electrolyte material layer; and
Via the solid electrolyte material layer from the positive electrode material layer side in a state in which a binding pressure of 100 MPa or more is applied to the primary assembly in the stacking direction of the positive electrode material layer, the solid electrolyte material layer, and the negative electrode material layer. Then, in the direction reaching the negative electrode material layer side, an energization step is performed such that the amount of electricity is 910 mAh or more per 1 g of Si simple substance powder contained in the negative electrode material layer, and Li ions are inserted into the negative electrode material layer. The manufacturing method of the electrode member for all-solid-state batteries is provided.
本開示の上記製造方法では、負極活物質としてＳｉ単体粒子を含み且つ結着材及び固体電解質を含まない負極材料部を用いることにより、体積当たりの理論容量が大きいＳｉ系材料からなる負極活物質を高密度に含む負極が形成されるため、電池全体としてのエネルギー密度が高い全固体電池用電極部材を得ることができる。 In the manufacturing method of the present disclosure, a negative electrode active material composed of a Si-based material having a large theoretical capacity per volume by using a negative electrode material portion that includes Si simple particles and does not include a binder and a solid electrolyte as a negative electrode active material. Therefore, an electrode member for an all-solid battery having a high energy density as a whole battery can be obtained.
また、本開示の上記製造方法では、前記１次組立体を、当該１次組立体に含まれる正極材料部、固体電解質材料部及び負極材料部の配列方向に高い拘束圧を印加した状態で、当該正極材料部側から当該固体電解質材料部を経由して当該負極材料部側に至る方向へ、一定量以上の電気量となるように通電することで、Ｓｉ系材料の粒子同士が接着するため、負極中に結着材及び固体電解質を含まないにもかかわらず、Ｓｉ系材料の粒子相互の接触性が向上し、充分な電池性能を得ることができる。
したがって、本開示の全固体電池用電極部材の製造方法によれば、Ｓｉ系材料からなる活物質を含む負極を有し、エネルギー密度が高く、負極内においてＳｉ系材料からなる活物質の粒子相互の接触性が良好な全固体電池用電極部材が得られる。
In the manufacturing method of the present disclosure, in the state where the primary assembly is applied with a high restraint pressure in the arrangement direction of the positive electrode material portion, the solid electrolyte material portion, and the negative electrode material portion included in the primary assembly, Since the particles of the Si-based material are bonded to each other by energizing the positive electrode material part side through the solid electrolyte material part to reach the negative electrode material part side so as to have a certain amount of electricity. Even though the negative electrode does not contain a binder and a solid electrolyte, the contact between the particles of the Si-based material is improved, and sufficient battery performance can be obtained.
Therefore, according to the method for manufacturing an electrode member for an all solid state battery of the present disclosure, the negative electrode containing an active material made of Si-based material has a high energy density, and the active material particles made of Si-based material in the negative electrode Thus, an electrode member for an all-solid-state battery having good contact property is obtained.
以下、本開示の全固体電池用電極部材の製造方法について詳細に説明する。
Ａ．製造方法の概略
図１Ａ〜図１Ｄは、本開示の全固体電池用電極部材の製造方法を概念的に示す図である。
先ず図１Ａ（準備工程）に示すように、Ｌｉを含有する正極活物質を含む正極材料部３、負極活物質としてＳｉ単体粉末を含み且つ結着材及び固体電解質を含まない負極材料部２、並びに、前記正極材料部と前記負極材料部の間に配置された固体電解質材料部１を備えた１次組立体１０１を準備する準備工程を行う。この１次組立体１０１は、正極材料部３、固体電解質材料部１及び負極材料部２が、この順序で配列された配列構造を有する。
次に、図１Ｂ（通電工程）に示すように、前記１次組立体１０１に、前記正極材料部３、前記固体電解質材料部１及び前記負極材料部２の配列方向に１００ＭＰａ以上の拘束圧を印加した状態で、前記正極材料部３側から前記固体電解質材料部１を経由して前記負極材料部２側に至る方向へ、負極材料部２に含まれるＳｉ単体粉末１ｇ当たり９１０ｍＡｈ以上の電気量となるように通電して、前記負極材料部２にＬｉイオンを挿入することにより、図１Ｃに示すように、正極６、負極５及び前記正極６と前記負極５の間に接合された固体電解質層４を有する、電極部材（正極−固体電解質層−負極集合体）１０２が得られる。
次に、図１Ｄに示すように、電極部材１０２に他の部材７を取り付けることにより全固体電池１０３が得られる。
Hereafter, the manufacturing method of the electrode member for all-solid-state batteries of this indication is demonstrated in detail.
A. Outline of Manufacturing Method FIGS. 1A to 1D are diagrams conceptually showing a manufacturing method of an electrode member for an all solid state battery of the present disclosure.
First, as shown in FIG. 1A (preparation step), a positive electrode material part 3 containing a positive electrode active material containing Li, a negative electrode material part 2 containing a simple substance Si powder as a negative electrode active material and not containing a binder and a solid electrolyte, And the preparatory process which prepares the primary assembly 101 provided with the solid electrolyte material part 1 arrange | positioned between the said positive electrode material part and the said negative electrode material part is performed. The primary assembly 101 has an arrangement structure in which the positive electrode material portion 3, the solid electrolyte material portion 1, and the negative electrode material portion 2 are arranged in this order.
Next, as shown in FIG. 1B (energization process), a restraining pressure of 100 MPa or more is applied to the primary assembly 101 in the arrangement direction of the positive electrode material portion 3, the solid electrolyte material portion 1, and the negative electrode material portion 2. In the applied state, the amount of electricity of 910 mAh or more per 1 g of Si powder contained in the negative electrode material part 2 from the positive electrode material part 3 side to the negative electrode material part 2 side via the solid electrolyte material part 1 As shown in FIG. 1C, the positive electrode 6, the negative electrode 5, and the solid electrolyte joined between the positive electrode 6 and the negative electrode 5 are inserted into the negative electrode material portion 2. An electrode member (positive electrode-solid electrolyte layer-negative electrode assembly) 102 having the layer 4 is obtained.
Next, as shown in FIG. 1D, an all-solid battery 103 is obtained by attaching another member 7 to the electrode member 102.
図２Ａ〜図２Ｉは、本開示の全固体電池用電極部材の製造方法の一実施形態を概念的に示す図である。
先ず図２Ａに示すように、固体電解質の粉末（固体電解質粉末１’）を加圧成形することにより、図２Ｂに示すように、固体電解質材料層（固体電解質材料部１）を成形する。
次に図２Ｃに示すように、前記固体電解質材料層の一面側に負極材料の粉末（負極材料粉末２’、これを「負極用合材」ということもある。）を堆積し、加圧成形することにより、図２Ｄに示すように、固体電解質材料層の上に負極材料層（負極材料部２）を成形する。
次に図２Ｅに示すように、前記固体電解質材料層の他の一面側に正極材料の粉末（正極材料粉末３’、これを「正極用合材」ということもある。）を堆積し、加圧成形することにより、図２Ｆに示すように、固体電解質材料層の前記負極材料層とは反対側の面に、正極材料層（正極材料部３）を成形する。
2A to 2I are diagrams conceptually illustrating an embodiment of a method for manufacturing an electrode member for an all-solid battery according to the present disclosure.
First, as shown in FIG. 2A, a solid electrolyte powder (solid electrolyte powder 1 ′) is pressure-molded to form a solid electrolyte material layer (solid electrolyte material portion 1) as shown in FIG. 2B.
Next, as shown in FIG. 2C, a negative electrode material powder (negative electrode material powder 2 ′, which may be referred to as “negative electrode mixture”) is deposited on one side of the solid electrolyte material layer, and pressure molding is performed. By doing so, as shown in FIG. 2D, a negative electrode material layer (negative electrode material portion 2) is formed on the solid electrolyte material layer.
Next, as shown in FIG. 2E, a positive electrode material powder (positive electrode material powder 3 ′, which may be referred to as “positive electrode mixture”) is deposited on the other surface of the solid electrolyte material layer and added. By pressure forming, as shown in FIG. 2F, a positive electrode material layer (positive electrode material portion 3) is formed on the surface of the solid electrolyte material layer opposite to the negative electrode material layer.
上記した一連の工程を経ると、図２Ｆに示すように、１次組立体１０１が得られる。この例の１次組立体１０１は、正極材料層、負極材料層、及び、前記正極材料層と前記負極材料層の間に固体電解質材料層が接合した構造を有する積層体（正極材料部−固体電解質材料部−負極材料部集合体）の形態をとっている。
この１次組立体１０１を、図２Ｇに示すように、正極材料層、固体電解質材料層及び負極材料層の積層方向に１００ＭＰａ以上の拘束圧を印加した状態で、前記正極材料層側から固体電解質材料層を経由して前記負極材料層側へ、負極材料層に含まれるＳｉ単体粉末１ｇ当たり９１０ｍＡｈ以上の電気量となるように通電することにより、前記負極材料層にＬｉイオンを挿入する。
この通電を行うことにより、図２Ｈに示すように、正極６、負極５及び前記正極６と前記負極５の間に接合された固体電解質層４を有する、電極部材１０２が得られる。
次に、図２Ｉに示すように、電極部材１０２に、集電体、外装体等の他の部材７を取り付けることにより、全固体電池１０３が得られる。
Through the series of steps described above, the primary assembly 101 is obtained as shown in FIG. 2F. The primary assembly 101 in this example includes a positive electrode material layer, a negative electrode material layer, and a laminate (positive electrode material portion-solid) having a structure in which a solid electrolyte material layer is bonded between the positive electrode material layer and the negative electrode material layer. Electrolyte material part-negative electrode material part aggregate).
As shown in FIG. 2G, in the primary assembly 101, a solid electrolyte is applied from the positive electrode material layer side in a state where a binding pressure of 100 MPa or more is applied in the stacking direction of the positive electrode material layer, the solid electrolyte material layer, and the negative electrode material layer. Li ions are inserted into the negative electrode material layer by energizing the negative electrode material layer through the material layer so that the amount of electricity is 910 mAh or more per gram of Si simple substance powder contained in the negative electrode material layer.
By conducting this energization, as shown in FIG. 2H, an electrode member 102 having a positive electrode 6, a negative electrode 5, and a solid electrolyte layer 4 bonded between the positive electrode 6 and the negative electrode 5 is obtained.
Next, as shown in FIG. 2I, an all-solid battery 103 is obtained by attaching another member 7 such as a current collector or an exterior body to the electrode member 102.
Ｂ．準備工程
（１）負極材料部
本開示の製造方法において、負極材料部は、負極活物質としてＳｉ単体粉末を含み、結着材及び固体電解質を含まず、必要に応じ、他の成分を含む。電池のエネルギー密度を上げる観点から、負極材料部はＳｉ単体粉末のみ含んでいてもよい。
Ｓｉ単体粉末を構成するＳｉ単体の粒子は、平均粒径（Ｄ５０）が通常１０ｎｍ以上５０μｍ以下の範囲内、さらに５０ｎｍ以上５μｍ以下の範囲内である。粒子の平均粒径が小さすぎると、取り扱い性が悪くなる可能性があり、粒子の平均粒径が大きすぎると、平坦な負極材料部を得るのが困難になる場合がある。Ｓｉ単体粒子同士の接触性を十分に高くする観点から、Ｓｉ単体粒子の平均粒径は、１μｍ以下、特に１００ｎｍ以下であってもよい。
負極材料部中のＳｉ単体粉末の割合は、特に限定されるものではないが、活物質をできるだけ多く充填する観点から、例えば５０質量％以上であり、６０質量％以上１００質量％以下の範囲内であってもよく、７０質量％以上１００質量％以下の範囲内であってもよく、１００質量％であってもよい。
B. Preparatory process (1) Negative electrode material part In the manufacturing method of this indication, a negative electrode material part contains Si simple substance powder as a negative electrode active material, does not contain a binder and a solid electrolyte, and contains another component as needed. From the viewpoint of increasing the energy density of the battery, the negative electrode material portion may contain only Si simple powder.
The Si simple particles constituting the Si simple powder have an average particle diameter (D 50 ) usually in the range of 10 nm to 50 μm, and more preferably in the range of 50 nm to 5 μm. If the average particle size of the particles is too small, the handleability may be deteriorated. If the average particle size of the particles is too large, it may be difficult to obtain a flat negative electrode material part. From the viewpoint of sufficiently increasing the contact between the Si simple particles, the average particle size of the Si simple particles may be 1 μm or less, particularly 100 nm or less.
Although the ratio of the Si simple substance powder in the negative electrode material part is not particularly limited, it is, for example, 50% by mass or more and within the range of 60% by mass to 100% by mass from the viewpoint of filling the active material as much as possible. It may be within a range of 70% by mass or more and 100% by mass or less, or 100% by mass.
負極材料部は、他の成分として導電材を含んでいてもよい。当該導電材としては、アセチレンブラック、ケッチェンブラック、カーボンファイバー等の炭素材料を挙げることができる。
前記負極材料部を形成するための材料（最終的に、負極を形成するための材料）、すなわち負極用合材は、電池のエネルギー密度を高くする観点から、典型的にはＳｉ単体粉末のみ含有するが、必要に応じＳｉ単体粉末以外の成分を含んでいてもよく、例えば、負極材料部を形成する途中で除去される成分を含んでいてもよい。
負極用合材中に含まれるが、負極材料部を形成する途中で除去される成分としては、溶剤や除去可能な結着材が挙げられる。
除去可能な結着材としては、負極用合材層を形成するときには結着材として機能するが、負極用合材層を焼成することにより分解又は揮散等し除去され、結着材を含まない負極材料部とすることができる結着材を用いることができる。そのような除去可能な結着材としては、ポリビニルブチラール、アクリル樹脂等が挙げられる。
The negative electrode material part may contain a conductive material as another component. Examples of the conductive material include carbon materials such as acetylene black, ketjen black, and carbon fiber.
The material for forming the negative electrode material part (finally, the material for forming the negative electrode), that is, the negative electrode mixture typically contains only Si simple powder from the viewpoint of increasing the energy density of the battery. However, components other than the Si simple substance powder may be included as necessary, for example, components that are removed during the formation of the negative electrode material portion may be included.
Examples of the component that is contained in the negative electrode composite material but is removed in the course of forming the negative electrode material portion include a solvent and a removable binder.
As a removable binder, it functions as a binder when forming a negative electrode mixture layer, but it is removed by decomposition or volatilization, etc. by firing the negative electrode mixture layer, and does not contain a binder. A binder that can be used as a negative electrode material portion can be used. Examples of such a removable binder include polyvinyl butyral and acrylic resin.
負極材料部を形成する方法としては、Ｓｉ単体粉末を含む負極用合材の粉末を加圧成形する方法が挙げられる。
Ｓｉ単体粉末を含む負極用合材の粉末を加圧成形する場合には、通常、１ＭＰａ以上４００ＭＰａ以下程度のプレス圧を負荷する。
その他の方法としては、例えば、Ｓｉ単体粉末及び除去可能な結着材を含む負極用合材の粉末を加圧成形して負極用合材層を形成した後、焼成することにより結着材を除去する方法や、Ｓｉ単体粉末、溶剤及び除去可能な結着材を含む負極用合材の分散液を固体電解質材料部の上又は他の支持体の上に塗布、乾燥して負極用合材層を形成した後、焼成することにより結着材を除去する方法などを行うことができる。
Examples of the method for forming the negative electrode material part include a method of pressure-molding a negative electrode composite material powder containing Si simple substance powder.
When pressure-molding the negative electrode composite material powder containing the Si simple substance powder, a press pressure of about 1 MPa or more and 400 MPa or less is usually applied.
Other methods include, for example, forming a negative electrode composite layer by pressure-molding a negative electrode composite powder containing Si simple substance powder and a removable binder, and then firing the binder. A negative electrode mixture containing a simple substance powder, a solvent and a removable binder containing a removable binder on a solid electrolyte material portion or other support and drying. After the layer is formed, a method of removing the binder by firing can be performed.
（２）正極材料部
正極材料部は、Ｌｉを含有する正極活物質を含み、必要に応じ、結着材、固体電解質、及び導電材等の他の成分を含む。
本開示においてＬｉを含有する正極活物質は、Ｌｉ元素を含む活物質であれば特に制限されるものではなく、単体状態のＬｉに限られず、リチウム化合物であってもよい。対極との関係で電池化学反応上の正極として機能し、Ｌｉイオンの移動を伴う電池化学反応を進行させる物質であれば、特に制限されず正極活物質として用いることができ、従来リチウムイオン電池の正極活物質として知られている物質も、本開示において用いることができる。
正極活物質としては例えば、リチウム単体金属、リチウム合金及びリチウム含有金属酸化物が挙げられる。リチウム合金としては、例えば、Ｉｎ−Ｌｉ合金等を用いることができる。リチウム含有金属酸化物としては、例えば、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＶＯ２、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２等の岩塩層状型活物質、ＬｉＭｎ２Ｏ４、Ｌｉ（Ｎｉ０．５Ｍｎ１．５）Ｏ４等のスピネル型活物質、ＬｉＦｅＰＯ４、ＬｉＭｎＰＯ４、ＬｉＮｉＰＯ４、ＬｉＣｏＰＯ４等のオリビン型活物質等を挙げることができる。
前記正極活物質の形状は特に限定されないが、膜状であっても粒子状であってもよい。
正極材料部中の正極活物質の割合は、特に限定されるものではないが、例えば５０質量％以上であり、６０質量％以上１００質量％以下の範囲内であってもよく、７０質量％以上１００質量％以下の範囲内であってもよい。
(2) Positive electrode material part A positive electrode material part contains the positive electrode active material containing Li, and contains other components, such as a binder, a solid electrolyte, and a electrically conductive material, as needed.
In the present disclosure, the positive electrode active material containing Li is not particularly limited as long as it is an active material containing Li element, and is not limited to Li in a single state, and may be a lithium compound. Any material that functions as a positive electrode on the battery chemical reaction in relation to the counter electrode and that promotes the battery chemical reaction accompanied by the movement of Li ions can be used as a positive electrode active material without any particular limitation. Materials known as positive electrode active materials can also be used in the present disclosure.
Examples of the positive electrode active material include lithium simple metals, lithium alloys, and lithium-containing metal oxides. As the lithium alloy, for example, an In—Li alloy or the like can be used. Examples of the lithium-containing metal oxide include rock salt layer type active materials such as LiCoO 2 , LiNiO 2 , LiVO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMn 2 O 4 , Li (Ni 0). .5 Mn 1.5) spinel active material O 4 or the like, can be cited LiFePO 4, LiMnPO 4, LiNiPO 4, LiCoPO olivine active material such as 4.
The shape of the positive electrode active material is not particularly limited, but may be a film shape or a particle shape.
The ratio of the positive electrode active material in the positive electrode material part is not particularly limited, but is, for example, 50% by mass or more, may be in the range of 60% by mass to 100% by mass, and is 70% by mass or more. It may be within a range of 100% by mass or less.
前記結着材としては、例えば、ポリフッ化ビニリデン（ＰＶｄＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ブチレンゴム（ＢＲ）、スチレン−ブタジエンゴム（ＳＢＲ）、ポリビニルブチラール（ＰＶＢ）、アクリル樹脂等を用いることができる。
前記導電材としては、前記負極材料部に用いるものと同様のものを用いることができる。
前記固体電解質としては、固体電解質結晶、非晶性固体電解質、固体電解質ガラスセラミックスのいずれであってもよく、後述する固体電解質材料部に用いられる固体電解質と同様のものを用いることができる。
Examples of the binder include polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), butylene rubber (BR), styrene-butadiene rubber (SBR), polyvinyl butyral (PVB), and an acrylic resin. it can.
As the conductive material, the same material as that used for the negative electrode material portion can be used.
The solid electrolyte may be any of a solid electrolyte crystal, an amorphous solid electrolyte, and a solid electrolyte glass ceramic, and the same solid electrolyte used for a solid electrolyte material part described later can be used.
正極材料部を形成するための材料（最終的に、正極を形成するための材料）、すなわち正極用合材は、さらに、正極材料部を形成する途中で除去される成分を含んでいてもよい。
正極用合材中に含まれるが、正極材料部を形成する途中で除去される成分としては、負極用合材に含有させることができる溶剤や除去可能な結着材と同様の成分が挙げられる。
正極材料部を形成する方法としては、負極材料部を形成する方法と同様の方法が挙げられる。
The material for forming the positive electrode material part (finally, the material for forming the positive electrode), that is, the positive electrode mixture may further contain a component that is removed during the formation of the positive electrode material part. .
The components that are contained in the positive electrode mixture but are removed during the formation of the positive electrode material portion include the same components as the solvent that can be contained in the negative electrode mixture and the removable binder. .
Examples of the method for forming the positive electrode material part include the same method as the method for forming the negative electrode material part.
（３）固体電解質材料部
固体電解質材料部は、固体電解質を含み、必要に応じ、他の成分を含む。
固体電解質としては、Ｌｉイオンの伝導度が高い酸化物系固体電解質、硫化物系固体電解質等が挙げられる。
前記酸化物系固体電解質としては、例えばＬｉ６．２５Ｌａ３Ｚｒ２Ａｌ０．２５Ｏ１２、Ｌｉ３ＰＯ４、ＬｉＰＯＮ等が挙げられ、前記硫化物系固体電解質としては、例えばＬｉ７Ｐ３Ｓ１１、Ｌｉ３ＰＳ４、Ｌｉ８Ｐ２Ｓ９、Ｌｉ１３ＧｅＰ３Ｓ１６、Ｌｉ１０ＧｅＰ２Ｓ１２等が挙げられる。
固体電解質材料部を形成するための固体電解質として、粉末状の固体電解質を用いてもよく、その場合に粉末を構成する固体電解質粒子の平均粒径（Ｄ５０）は、通常１０ｎｍ以上５０μｍ以下の範囲内、さらに５０ｎｍ以上１０μｍ以下の範囲内である。
(3) Solid electrolyte material part A solid electrolyte material part contains a solid electrolyte and contains other components as needed.
Examples of the solid electrolyte include oxide solid electrolytes and sulfide solid electrolytes having high Li ion conductivity.
Examples of the oxide solid electrolyte include Li 6.25 La 3 Zr 2 Al 0.25 O 12 , Li 3 PO 4 , and LiPON. Examples of the sulfide solid electrolyte include Li 7 P 3. S 11, Li 3 PS 4, Li 8 P 2 S 9, Li 13 GeP 3 S 16, Li 10 GeP 2 S 12 , and the like.
As the solid electrolyte for forming the solid electrolyte material part, a powdered solid electrolyte may be used, and in that case, the average particle diameter (D 50 ) of the solid electrolyte particles constituting the powder is usually 10 nm or more and 50 μm or less. Within the range, and further within the range of 50 nm to 10 μm.
前記固体電解質は、１種単独で、又は２種以上のものを用いることができる。また、２種以上の固体電解質を用いる場合、２種以上の固体電解質を混合してもよく、又は２層以上の固体電解質それぞれの層を形成して多層構造としてもよい。
固体電解質を２層構造とする場合には、例えば、正極側に硫化物固体電解質、負極側に酸化物固体電解質を配置してもよいし、その逆の順序で配置してもよい。固体電解質の電位窓に対応した配置であれば、どのような配置順序にしてもよい。
固体電解質材料部中の固体電解質の割合は、特に限定されるものではないが、例えば５０質量％以上であり、６０質量％以上１００質量％以下の範囲内であってもよく、７０質量％以上１００質量％以下の範囲内であってもよく、１００質量％であってもよい。
固体電解質材料部に含まれる他の成分としては、バインダー、可塑剤、分散剤等が挙げられる。
The solid electrolyte can be used alone or in combination of two or more. When two or more kinds of solid electrolytes are used, two or more kinds of solid electrolytes may be mixed, or two or more solid electrolyte layers may be formed to form a multilayer structure.
When the solid electrolyte has a two-layer structure, for example, a sulfide solid electrolyte may be disposed on the positive electrode side and an oxide solid electrolyte may be disposed on the negative electrode side, or vice versa. Any arrangement order may be employed as long as the arrangement corresponds to the potential window of the solid electrolyte.
The ratio of the solid electrolyte in the solid electrolyte material part is not particularly limited, but is, for example, 50% by mass or more, may be in the range of 60% by mass to 100% by mass, and is 70% by mass or more. It may be within a range of 100% by mass or less, or 100% by mass.
Examples of other components contained in the solid electrolyte material part include a binder, a plasticizer, and a dispersant.
固体電解質材料部を形成する方法としては、固体電解質及び必要に応じ他の成分を含む固体電解質材料の粉末を加圧成形する方法が挙げられる。固体電解質材料の粉末を加圧成形する場合には、通常、負極用合材の粉末を加圧成形する場合と同様に、１ＭＰａ以上４００ＭＰａ以下程度のプレス圧を負荷する。
また、他の方法としては、固体電解質及び必要に応じ他の成分を含有する固体電解質材料の溶液又は分散液を用いたキャスト成膜法などを行うことができる。
Examples of the method for forming the solid electrolyte material portion include a method in which a powder of the solid electrolyte material containing the solid electrolyte and other components as necessary is pressure-molded. When pressure-molding the powder of the solid electrolyte material, a press pressure of about 1 MPa or more and 400 MPa or less is usually applied as in the case of pressure-molding the powder of the negative electrode mixture.
Moreover, as another method, the cast film-forming method using the solution or dispersion liquid of the solid electrolyte material which contains a solid electrolyte and another component as needed can be performed.
（４）１次組立体
本開示において１次組立体は、正極材料部、固体電解質材料部、及び、負極材料部がこの順序で配列され、直接または他の材料からなる部分を介して接合しており、さらに、正極材料部上の固体電解質材料部が存在する位置とは反対側（正極材料部の外方側）、及び、負極材料部上の固体電解質材料部が存在する位置とは反対側（負極材料部の外方側）のうちの片方又は両方の側に、他の材料からなる部分が接合していてもよい配列構造を有する各部の集合体（正極材料部−固体電解質材料部−負極材料部集合体）である。
前記１次組立体は、後述の通電工程において、均一に拘束圧を負荷しながら、正極材料部側から固体電解質材料部を経由して負極材料部側に至る方向へ通電できる限り、他の材料からなる部分が付属していてもよい。正極材料部と固体電解質材料部の間には、例えば、ＬｉＮｂＯ３、Ｌｉ４Ｔｉ５Ｏ１２、Ｌｉ３ＰＯ４のような被覆層が設けられていても良く、負極材料部と固体電解質材料部の間にも、同様の被覆層が設けられていても良い。
正極材料部の外方側及び負極材料部の外方側のいずれか一方又は両方の側には、例えば、集電体や外装体が後述する通電工程における通電前に付属していてもよい。
上記１次組立体は、典型的には、正極材料部、負極材料部、及び、前記正極材料部と前記負極材料部の間に配置された固体電解質材料部が直接接合し、且つ、正極材料部の外方側及び負極材料部の外方側のいずれにも他の材料からなる部分が接合していない配列構造を有する集合体である。
(4) Primary assembly In the present disclosure, the primary assembly includes a positive electrode material portion, a solid electrolyte material portion, and a negative electrode material portion arranged in this order, and is joined directly or via a portion made of another material. Furthermore, the position opposite to the position where the solid electrolyte material portion exists on the positive electrode material portion (outside of the positive electrode material portion) and the position where the solid electrolyte material portion exists on the negative electrode material portion An assembly of each part having an array structure in which a part made of another material may be joined to one or both of the sides (outside of the negative electrode material part) (positive electrode material part-solid electrolyte material part) Negative electrode material part assembly).
As long as the primary assembly can be energized in a direction from the positive electrode material part side to the negative electrode material part side through the solid electrolyte material part while uniformly applying a restraining pressure in the energization process described later, other materials are used. The part which consists of may be attached. Between the positive electrode material part and the solid electrolyte material part, for example, a coating layer such as LiNbO 3 , Li 4 Ti 5 O 12 , Li 3 PO 4 may be provided. The negative electrode material part and the solid electrolyte material part A similar coating layer may be provided between the two.
For example, a current collector or an exterior body may be attached to one or both of the outer side of the positive electrode material part and the outer side of the negative electrode material part before energization in an energization process described later.
In the primary assembly, typically, a positive electrode material part, a negative electrode material part, and a solid electrolyte material part arranged between the positive electrode material part and the negative electrode material part are directly joined, and the positive electrode material This is an assembly having an array structure in which parts made of other materials are not joined to either the outer side of the part or the outer side of the negative electrode material part.
上記１次組立体を作製する方法の一つとして、図２Ａ〜図２Ｉに示した方法がある。すなわち、固体電解質材料の粉末、負極材料の粉末、及び、正極材料の粉末を用い、固体電解質材料の粉体加圧成形を行うことにより固体電解質材料部を形成し、固体電解質材料部の一面上での負極材料の粉末の粉体加圧成形、及び、固体電解質材料部の負極材料を形成した面とは反対側の面上での正極材料の粉末の粉体加圧成形を順次行う方法である。
この場合、固体電解質材料の粉末、負極材料の粉末及び正極材料の粉末を加圧成形する際のプレス圧は、通常１ＭＰａ以上６００ＭＰａ以下程度である。
ただし、上記１次組立体を作製する方法は、図２Ａ〜図２Ｉの方法に限定されない。
例えば、粉体加圧成形の加圧シリンダー内に、Ｓｉ単体粉末を含む負極材料の粉末を投入し均一な厚みに堆積して負極材料粉末堆積層を形成する。
上記負極材料粉末堆積層の上に、固体電解質粉末及び必要に応じ他の成分を含む固体電解質材料の粉末を投入し均一な厚みに堆積して固体電解質材料粉末層を形成する。
上記固体電解質材料粉末層の上に、Ｌｉを含有する正極活物質を含む材料の粉末を投入し均一な厚みに堆積して正極材料粉末層を形成する。
その後、このようにして形成された３層の粉末堆積層を有する粉末堆積体を一度に加圧成形することにより、１次組立体を作製してもよい。
また、固体電解質材料部、負極材料部、及び、正極材料部は、粉体加圧成形以外の手法で作製してもよい。具体的な方法は、本明細書中で上記したとおりである。例えば、固体電解質材料部は、固体電解質を含む固体電解質材料の溶液又は分散液を用いたキャスト成膜法により成形してもよい。負極材料部及び正極材料部は、例えば、負極材料の粉末又は正極材料の粉末、及び、除去可能な結着材を含む分散液を固体電解質材料部の上に塗布することにより塗膜を形成した後、この塗膜を加熱して塗膜から結着材を除去する方法や、あるいは、負極材料の粉末又は正極材料の粉末、及び、除去可能な結着材を含む粉末を加圧成形して正極材料部又は負極材料部の形状とした後、この成形体を加熱して塗膜から結着材を除去する方法により形成してもよい。
また、負極材料部及び正極材料部は、固体電解質材料部以外の支持体上に形成してもよい。その場合、当該支持体から負極材料部及び正極材料部を剥離し、剥離した負極材料部又は正極材料部を、固体電解質材料部の上に接合する。
One method for producing the primary assembly is shown in FIGS. 2A to 2I. That is, a solid electrolyte material part is formed by performing powder pressure molding of a solid electrolyte material using a powder of a solid electrolyte material, a powder of a negative electrode material, and a powder of a positive electrode material, and on one side of the solid electrolyte material part In this method, the powder pressure molding of the negative electrode material powder and the powder pressure molding of the positive electrode material powder on the surface of the solid electrolyte material portion opposite to the surface on which the negative electrode material is formed are sequentially performed. is there.
In this case, the press pressure when the solid electrolyte material powder, the negative electrode material powder and the positive electrode material powder are pressure-molded is usually about 1 MPa to 600 MPa.
However, the method of manufacturing the primary assembly is not limited to the method of FIGS. 2A to 2I.
For example, a negative electrode material powder containing Si simple substance powder is put into a pressure cylinder of powder pressure molding and deposited to a uniform thickness to form a negative electrode material powder deposition layer.
On the negative electrode material powder deposition layer, a solid electrolyte powder and a solid electrolyte material powder containing other components as necessary are deposited and deposited to a uniform thickness to form a solid electrolyte material powder layer.
A powder of a material containing a positive electrode active material containing Li is placed on the solid electrolyte material powder layer and deposited to a uniform thickness to form a positive electrode material powder layer.
Thereafter, the primary assembly may be manufactured by press-molding the powder deposit having the three powder deposit layers thus formed at once.
Moreover, you may produce a solid electrolyte material part, a negative electrode material part, and a positive electrode material part by methods other than powder pressure molding. The specific method is as described above in this specification. For example, the solid electrolyte material portion may be formed by a cast film forming method using a solution or dispersion of a solid electrolyte material containing a solid electrolyte. The negative electrode material part and the positive electrode material part were formed, for example, by applying a dispersion containing negative electrode material powder or positive electrode material powder and a removable binder onto the solid electrolyte material part. Then, this coating film is heated to remove the binder from the coating film, or the negative electrode material powder or the positive electrode material powder and the powder containing the removable binder material are pressure-molded. After forming the shape of the positive electrode material part or the negative electrode material part, the formed body may be heated to remove the binder from the coating film.
The negative electrode material part and the positive electrode material part may be formed on a support other than the solid electrolyte material part. In that case, the negative electrode material part and the positive electrode material part are peeled from the support, and the peeled negative electrode material part or positive electrode material part is bonded onto the solid electrolyte material part.
Ｃ．通電工程
本開示の製造方法において、通電工程は、１次組立体に対して、当該１次組立体に含まれる正極材料部、固体電解質材料部及び負極材料部の配列方向に１００ＭＰａ以上の拘束圧を印加した状態で、当該１次組立体の正極材料部側から固体電解質材料部を経由して負極材料部側に至る方向へ通電して、負極材料部に含まれるＳｉ単体粉末１ｇ当たり、９１０ｍＡｈ以上の電気量となるように通電することにより、前記負極材料部にＬｉイオンを挿入する工程である。
負極材料部にＬｉイオンを挿入することにより、Ｓｉ単体の粒子同士が接着し、負極が作製される。
C. Energization process In the manufacturing method of the present disclosure, the energization process is performed with respect to the primary assembly at a constraint pressure of 100 MPa or more in the arrangement direction of the positive electrode material portion, the solid electrolyte material portion, and the negative electrode material portion included in the primary assembly. Is applied in the direction from the positive electrode material part side of the primary assembly to the negative electrode material part side through the solid electrolyte material part, and 910 mAh per 1 g of Si simple substance powder contained in the negative electrode material part. This is a step of inserting Li ions into the negative electrode material part by energizing to have the above amount of electricity.
By inserting Li ions into the negative electrode material part, Si single particles are bonded to each other, and a negative electrode is produced.
ここで、「１次組立体に対して前記正極材料部側から前記固体電解質材料部を経由して前記負極材料部側に至る方向へ通電する」とは、図１Ｂに示すように、外部電源に電気抵抗体としての１次組立体１０１を接続するときに、外部電源の正極（電圧が高い側の端子）を１次組立体１０１の正極材料部３側に接続し、外部電源の負極（電圧が低い側の端子）を１次組立体１０１の負極材料部２側に接続し、電流を流すことを意味する。 Here, “the current is supplied to the primary assembly from the positive electrode material part side to the negative electrode material part side via the solid electrolyte material part” as shown in FIG. When connecting the primary assembly 101 as an electric resistor to the positive electrode (terminal on the higher voltage side) of the external power source is connected to the positive electrode material part 3 side of the primary assembly 101, and the negative electrode ( This means that a terminal having a low voltage) is connected to the negative electrode material part 2 side of the primary assembly 101 and a current is passed.
１次組立体に負荷する拘束圧は、１００ＭＰａ以上であればよいが、電極部材内部のラミネーションを防止する観点から、４００ＭＰａ以下であってもよい。
また１次組立体の通電量は、負極材料部に含まれるＳｉ単体粉末１ｇ当たり、９１０ｍＡｈ以上であればよいが、Ｓｉ単体粉末のＬｉ挿入容量の観点から、負極材料部に含まれるＳｉ単体粉末１ｇ当たり、４２００ｍＡｈ以下であってもよく、２１００ｍＡｈ以下であってもよい。
The restraint pressure applied to the primary assembly may be 100 MPa or more, but may be 400 MPa or less from the viewpoint of preventing lamination inside the electrode member.
Further, the energization amount of the primary assembly may be 910 mAh or more per 1 g of Si simple substance powder contained in the negative electrode material part, but from the viewpoint of the Li insertion capacity of the Si simple substance powder, the Si simple substance powder contained in the negative electrode material part It may be 4200 mAh or less per 1 g, or 2100 mAh or less.
上記通電工程により得られた負極の内部では、Ｌｉが挿入されることでＳｉ系材料の粒子が形状を変化させながら膨張する。その際に一定以上の拘束圧が印加されていると、負極内部の隙間を埋めるように粒子形状が変化するため、Ｓｉ粒子同士が接着する。
したがって、負極中に結着材及び固体電解質を含まないにもかかわらず、Ｓｉ系材料相互の接触性が向上し、充分な電池性能を得ることができる。
なお、Ｓｉ系材料の粒子が膨張する際に印加される拘束圧が十分でない場合には、Ｓｉ系材料の粒子同士の接着が不十分となる。
本開示において、Ｓｉ系材料の粒子同士が接着するとは、負極材料部の内部又は負極の内部に存在し、隣接し合うＳｉ系材料の粒子の接触界面（粒界部）が融合し、粒界の一部または全部が消失する現象をいう。
負極材料部に通電工程を行うことにより形成された負極の内部においてＳｉ系材料の粒子が接着していることは、本開示の製造方法により得られた全固体電池用電極部材を切断し、負極の切断面をＳＥＭ（走査電子顕微鏡）により観察することで確認することができる。
Inside the negative electrode obtained by the energization step, the Li-based material expands while the shape of the Si-based material particles changes as Li is inserted. In this case, if a certain pressure or more is applied, the shape of the particles changes so as to fill the gap inside the negative electrode, so that the Si particles adhere to each other.
Therefore, although the binder and the solid electrolyte are not included in the negative electrode, the contact property between the Si-based materials is improved, and sufficient battery performance can be obtained.
In addition, when the restraint pressure applied when the particle | grains of Si type material expand | swell is not enough, adhesion | attachment of particles of Si type material will become inadequate.
In the present disclosure, adhesion of Si-based material particles to each other means that the contact interface (grain boundary portion) between adjacent Si-based material particles is present inside the negative electrode material portion or inside the negative electrode, and the grain boundary A phenomenon in which part or all of the
The fact that the Si-based material particles are adhered inside the negative electrode formed by conducting an energization process in the negative electrode material part cuts the all-solid-state battery electrode member obtained by the manufacturing method of the present disclosure, It can confirm by observing the cut surface of this by SEM (scanning electron microscope).
上記したようなＳｉ系材料の粒子同士の接着状態は、１次組立体を、当該１次組立体に含まれる正極材料部、固体電解質材料部及び負極材料部の配列方向に高い拘束圧を印加した状態で、当該正極材料部側から当該固体電解質材料部を経由して当該負極材料部側へ一定量以上の電気量となるように通電することにより得られる。
１００ＭＰａ以上という拘束圧は非常に高い圧力である。例えば、上記特許文献１では、電池部材（本開示における１次組立体に相当する）に対し積層方向に１５０ｋｇｆ／ｃｍ２以上の拘束圧を印加した状態で、充放電処理を複数回行うことでＳｉ含有活物質層を製造することが記載されているが、「１５０ｋｇｆ／ｃｍ２以上の拘束圧」をＰａ単位に換算すると「１４．７０９８３ＭＰａ」になる。したがって本開示において設定された拘束圧は、特許文献１に記載された拘束圧と比べて格段に大きい値である。
＜計算式＞
前提条件：１ｋｇｆ／ｃｍ２＝９．８０６６５×１０４Ｐａ
したがって、
１５０ｋｇｆ／ｃｍ２
＝１５０×９．８０６６５×１０４Ｐａ
＝１．５×９．８０６６５×１０６Ｐａ
＝１．５×９．８０６６５ＭＰａ
≒１４．７０９８３ＭＰａ
The bonding state between the Si-based material particles as described above applies a high constraining pressure to the primary assembly in the arrangement direction of the positive electrode material portion, the solid electrolyte material portion, and the negative electrode material portion included in the primary assembly. In this state, it is obtained by energizing the positive electrode material part side through the solid electrolyte material part to the negative electrode material part side so as to have a certain amount of electricity.
The restraint pressure of 100 MPa or more is a very high pressure. For example, in Patent Document 1, charge / discharge treatment is performed a plurality of times in a state in which a constraint pressure of 150 kgf / cm 2 or more is applied to the battery member (corresponding to the primary assembly in the present disclosure) in the stacking direction. It is described that an Si-containing active material layer is produced, but when “restraint pressure of 150 kgf / cm 2 or more” is converted into Pa units, “14.70983 MPa” is obtained. Therefore, the restraint pressure set in the present disclosure is a value that is significantly larger than the restraint pressure described in Patent Document 1.
<Calculation formula>
Precondition: 1 kgf / cm 2 = 9.80665 × 10 4 Pa
Therefore,
150 kgf / cm 2
= 150 × 9.80665 × 10 4 Pa
= 1.5 × 9.80665 × 10 6 Pa
= 1.5 × 9.80665 MPa
≈ 14.70983 MPa
前記１次組立体に拘束圧を印加する方法としては、前記１次組立体に均等に拘束圧を印加することができる方法であれば特に制限されないが、例えば、油圧ポンプ（理研精機社製、Ｐ−６型）を用いて圧力を付加する方法が挙げられる。 The method for applying the restraining pressure to the primary assembly is not particularly limited as long as it can apply the restraining pressure evenly to the primary assembly. For example, a hydraulic pump (manufactured by Riken Seiki Co., Ltd., And a method of applying pressure using P-6 type).
Ｄ．全固体電池用電極部材及び全固体電池
上記１次組立体は、上記「Ｃ．通電工程」による通電を経て、正極−固体電解質層−負極集合体となる。
上記正極−固体電解質層−負極集合体は、正極、固体電解質層及び負極がこの順序で配列され、直接または他の材料からなる部分を介して接合しており、さらに、正極上の固体電解質層が存在する位置とは反対側（正極の外方側）、及び、負極上の固体電解質層が存在する位置とは反対側（負極の外方側）のうちの片方又は両方の側に、他の材料からなる部分が接合していてもよい配列構造を有する各部の集合体である。
正極−固体電解質層−負極集合体の正極と負極それぞれの厚みは、通常０．１μｍ以上１００μｍ以下程度であり、固体電解質層の厚みは、通常０．１μｍ以上１ｍｍ以下程度である。
上記の正極−固体電解質層−負極集合体に、集電体、外装体等の他の部材を取り付けることにより、全固体電池の機能的単位であるセルが得られ、複数のセルを集積して電気的に接続することにより、全固体電池が得られる。
すなわち、本開示における全固体電池は、初回充電後の状態のものとする概念である。
D. All-solid-state battery electrode member and all-solid-state battery The primary assembly becomes a positive electrode-solid electrolyte layer-negative electrode assembly through energization by the "C. energization step".
In the positive electrode-solid electrolyte layer-negative electrode assembly, the positive electrode, the solid electrolyte layer, and the negative electrode are arranged in this order, and joined directly or via a portion made of another material, and further, the solid electrolyte layer on the positive electrode On one side or both sides of the side opposite to the position where the negative electrode exists (the outer side of the positive electrode) and the side opposite the position where the solid electrolyte layer on the negative electrode exists (the outer side of the negative electrode) It is the aggregate | assembly of each part which has the arrangement | sequence structure in which the part which consists of these materials may join.
The thickness of each of the positive electrode and the negative electrode of the positive electrode-solid electrolyte layer-negative electrode assembly is usually about 0.1 μm to 100 μm, and the thickness of the solid electrolyte layer is usually about 0.1 μm to 1 mm.
By attaching other members such as a current collector and an outer package to the positive electrode-solid electrolyte layer-negative electrode assembly, a cell that is a functional unit of an all-solid battery is obtained, and a plurality of cells are integrated. By electrically connecting, an all-solid battery can be obtained.
That is, the all solid state battery in the present disclosure is a concept that assumes a state after the initial charge.
（固体電解質Ａの合成）
アルゴン雰囲気下のグローブボックス内で、Ｌｉ２Ｓ及びＰ２Ｓ５をモル比で４：１の組成となるように混合し、原料組成物を得た。次に、原料組成物１ｇを、ジルコニアボール（５ｍｍφ、８０個）とともに、ジルコニア製のポット（４５ｍｌ）に入れ、ポットを完全に密閉した（アルゴン雰囲気）。このポットを遊星型ボールミル機（フリッチュ・ジャパン社製Ｐ７）に取り付け、台盤回転数５００ｒｐｍで、２０時間メカニカルミリングを行った。これにより、固体電解質ＡとしてＬｉ８Ｐ２Ｓ９の粉末を得た。
(Synthesis of solid electrolyte A)
In a glove box under an argon atmosphere, Li 2 S and P 2 S 5 were mixed at a molar ratio of 4: 1 to obtain a raw material composition. Next, 1 g of the raw material composition was placed in a zirconia pot (45 ml) together with zirconia balls (5 mmφ, 80 pieces), and the pot was completely sealed (argon atmosphere). This pot was attached to a planetary ball mill (P7, manufactured by Fritsch Japan), and mechanical milling was performed at a base plate rotation speed of 500 rpm for 20 hours. Thereby, a powder of Li 8 P 2 S 9 was obtained as the solid electrolyte A.
（固体電解質Ｂの準備）
固体電解質Ｂとしては、直径φ１０ｍｍ、厚み０．５ｍｍのＬｉ６．２５Ｌａ３Ｚｒ２Ａｌ０．２５Ｏ１２（豊島製作所製）焼結体を用いた。
(Preparation of solid electrolyte B)
As the solid electrolyte B, a Li 6.25 La 3 Zr 2 Al 0.25 O 12 (manufactured by Toshima Seisakusho) sintered body having a diameter of 10 mm and a thickness of 0.5 mm was used.
［実施例１］
（１次組立体の作製）
１．まず、固体電解質Ａの粉末１５０ｍｇを、ＰＥＴ製のシリンダに添加し、３．５ｔｏｎ／ｃｍ２（≒３４３ＭＰａ）でプレスし、固体電解質材料部を形成した。
２．全固体電池の正極活物質としては、ＬｉＣｏＯ２等のリチウム含有金属酸化物が現状では一般的であるが、本実施例では、本開示の電極部材の作用を示すモデルセルを作製するために、Ｉｎ箔（ニラコ社製φ１０ｍｍ、厚さ０．１ｍｍ）にＬｉ箔（本庄ケミカル社製）を貼付したＬｉＩｎ箔を用いた。当該ＬｉＩｎ箔を前記固体電解質材料部の一方の表面に配置し、続けて当該固体電解質材料部の他方の表面に、負極活物質であるＳｉ単体の粉末（Ａｌｆａ ａｅｓａｒ社製 平均粒径１００ｎｍ）を、単位面積当たりの添加量を０．６ｍｇ／ｃｍ２として堆積させ、固体電解質材料部、ＬｉＩｎ箔とあわせて５ｔｏｎ／ｃｍ２（≒４９０ＭＰａ）でプレスし、１次組立体を得た。
[Example 1]
(Preparation of primary assembly)
1. First, 150 mg of the solid electrolyte A powder was added to a cylinder made of PET and pressed at 3.5 ton / cm 2 (≈343 MPa) to form a solid electrolyte material part.
2. As a positive electrode active material of an all-solid-state battery, a lithium-containing metal oxide such as LiCoO 2 is generally used at present, but in this example, in order to produce a model cell showing the action of the electrode member of the present disclosure, A LiIn foil was used in which an Li foil (manufactured by Honjo Chemical Co., Ltd.) was attached to an In foil (manufactured by Niraco, φ10 mm, thickness 0.1 mm). The LiIn foil is disposed on one surface of the solid electrolyte material part, and subsequently, a powder of Si alone (an average particle size of 100 nm manufactured by Alfa aesar) as a negative electrode active material is applied to the other surface of the solid electrolyte material part. The amount added per unit area was 0.6 mg / cm 2 , and the solid electrolyte material part and LiIn foil were pressed together at 5 ton / cm 2 (≈490 MPa) to obtain a primary assembly.
（全固体電池用電極部材の作製）
得られた１次組立体を６Ｎｍのトルクでネジ締めすることにより、積層方向に１００ＭＰａの拘束圧を印加した状態で、０．１ｍＡ／ｃｍ２での電流密度でＳｉ単体粉末１ｇあたり２１００ｍＡｈを通電することにより、前記負極材料部にＬｉイオンを挿入し、全固体電池用電極部材を得た。
(Preparation of electrode member for all solid state battery)
By screwing the obtained primary assembly with a torque of 6 Nm, 2100 mAh was applied per 1 g of Si powder at a current density of 0.1 mA / cm 2 in a state where a binding pressure of 100 MPa was applied in the stacking direction. As a result, Li ions were inserted into the negative electrode material part to obtain an electrode member for an all solid state battery.
［実施例２］
（１次組立体の作製）
１．まず、固体電解質Ａの粉末１５０ｍｇを、ポリエチレンテレフタラート（ＰＥＴ）製のシリンダに添加し、３．５ｔｏｎ／ｃｍ２（≒３４３ＭＰａ）でプレスし、次に固体電解質Ｂの焼結体（φ１０ｍｍ×ｔ０．５ｍｍ）を、ポリエチレンテレフタラート（ＰＥＴ）製のシリンダ内に配置することで固体電解質材料部を形成した。
２．Ｉｎ箔（ニラコ社製φ１０ｍｍ、厚さ０．１ｍｍ）にＬｉ箔（本庄ケミカル社製）を貼付した正極材料部（ＬｉＩｎ箔）を用意し、固体電解質Ａ側の表面に配置し、続けて当該固体電解質Ｂ側の表面に、負極活物質であるＳｉ単体の粉末（Ａｌｆａ ａｅｓａｒ社製 平均粒径１００ｎｍ）を、単位面積当たりの添加量を０．６ｍｇ／ｃｍ２として堆積させ、固体電解質Ａ、固体電解質Ｂ、ＬｉＩｎ箔とあわせて５ｔｏｎ／ｃｍ２（≒４９０ＭＰａ）でプレスし、１次組立体を得た。
[Example 2]
(Preparation of primary assembly)
1. First, 150 mg of the solid electrolyte A powder was added to a polyethylene terephthalate (PET) cylinder, pressed at 3.5 ton / cm 2 (≈343 MPa), and then the solid electrolyte B sintered body (φ10 mm × t0 0.5 mm) was placed in a polyethylene terephthalate (PET) cylinder to form a solid electrolyte material part.
2. Prepare a positive electrode material part (LiIn foil) in which a Li foil (manufactured by Honjo Chemical Co., Ltd.) is attached to an In foil (Nilaco φ10 mm, thickness 0.1 mm), and place it on the surface of the solid electrolyte A side. On the surface of the solid electrolyte B side, a powder of a simple substance of Si as a negative electrode active material (average particle size 100 nm manufactured by Alfa aesar) was deposited with an addition amount per unit area of 0.6 mg / cm 2 , and solid electrolyte A, A primary assembly was obtained by pressing together with the solid electrolyte B and LiIn foil at 5 ton / cm 2 (≈490 MPa).
（全固体電池用電極部材の作製）
得られた１次組立体において、実施例１と同様に通電工程を行うことにより、実施例２の全固体電池用電極部材を得た。
(Preparation of electrode member for all solid state battery)
In the obtained primary assembly, an energization process was performed in the same manner as in Example 1 to obtain an electrode member for an all-solid-state battery of Example 2.
（比較例１〜４）
実施例１において、通電量を表１のように変更したこと以外は、実施例１と同様にして比較例１及び２の全固体電池用電極部材を作製した。
また、実施例２において、拘束圧、及び通電量を表１のように変更したこと以外は、実施例２と同様にして比較例３及び４の電極部材を作製した。
なお、比較例３と比較例４においては、電極部材としての抵抗が大きく、通電に時間がかかりすぎたため、表１に記載された通電量まで通電した時点で通電工程を中断した。
(Comparative Examples 1-4)
In Example 1, all-solid-state battery electrode members of Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the energization amount was changed as shown in Table 1.
Moreover, in Example 2, the electrode members of Comparative Examples 3 and 4 were produced in the same manner as in Example 2 except that the restraining pressure and the energization amount were changed as shown in Table 1.
In Comparative Example 3 and Comparative Example 4, since the resistance as an electrode member was large and it took too much time to energize, the energization process was interrupted when the energization amount shown in Table 1 was energized.
〔評価方法〕
得られた全固体電池用電極部材を切断し、ＳＥＭ（日本電子株式会社製の走査電子顕微鏡 ＪＳＭ−７８００Ｆ）を使用して負極の切断面のＳｉ粒子同士の接着を観察した。その結果、Ｓｉ粒子同士の接着が確認できたものを「○」、接着が確認できなかったものを「×」として表１に示す。
実施例１のＳＥＭ画像を図３に示す。
なお、比較例３及び４については、通電量が極端に少ないことからＬｉの挿入量が十分でなく、Ｓｉ粒子同士の接着も不十分であることが予測されるため、ＳＥＭ画像を確認せずに「×」と判断した。
〔Evaluation method〕
The obtained electrode member for an all-solid-state battery was cut, and adhesion between Si particles on the cut surface of the negative electrode was observed using an SEM (scanning electron microscope JSM-7800F manufactured by JEOL Ltd.). As a result, it was shown in Table 1 as “◯” when the adhesion between the Si particles was confirmed, and “X” when the adhesion could not be confirmed.
The SEM image of Example 1 is shown in FIG.
In Comparative Examples 3 and 4, since the amount of energization is extremely small, the insertion amount of Li is not sufficient, and the adhesion between Si particles is predicted to be insufficient, so the SEM image is not confirmed. Was judged as “×”.
［結果］
実施例１と比較例１〜２を比較すると、通電量が６３０ｍＡｈ／ｇ以下である場合には粒界の融合が十分に進行せず、Ｓｉ粒子同士の接着が不十分であることが分かった。
実施例２と比較例３〜４を比較すると、拘束圧が１００ＭＰａ未満である場合には粒界の融合が十分に進行せず、Ｓｉ粒子同士の接着が不十分であることが分かった。また、Ｓｉ粒子同士の接着の進行が遅いため、負極中の導電性が低いままの状態が継続し、電極部材全体としての抵抗が大きくなりすぎたと推測される。
[result]
When Example 1 was compared with Comparative Examples 1 and 2, it was found that when the energization amount was 630 mAh / g or less, the fusion of the grain boundaries did not proceed sufficiently, and the adhesion between the Si particles was insufficient. .
When Example 2 was compared with Comparative Examples 3 and 4, it was found that when the confining pressure was less than 100 MPa, the fusion of the grain boundaries did not proceed sufficiently, and the adhesion between the Si particles was insufficient. Moreover, since the progress of the adhesion between the Si particles is slow, it is presumed that the state in which the conductivity in the negative electrode remains low and the resistance as a whole of the electrode member becomes too large.
（比較例５）
１．まず、固体電解質Ａの粉末１５０ｍｇを、ＰＥＴ製のシリンダに添加し、３．５ｔｏｎ／ｃｍ２（≒３４３ＭＰａ）でプレスし、固体電解質材料部を形成した。
２．全固体電池の正極活物質としては、Ｉｎ箔（ニラコ社製φ１０ｍｍ、厚さ０．１ｍｍ）にＬｉ箔（本庄ケミカル社製）を貼付したＬｉＩｎ箔を用いた。当該ＬｉＩｎ箔を前記固体電解質材料部の一方の表面に配置し、続けて当該固体電解質材料部の他方の表面に、負極活物質であるＳｉ単体の粉末（Ａｌｆａ ａｅｓａｒ社製 平均粒径１００ｎｍ）を、単位面積当たりの添加量を０．９ｍｇ／ｃｍ２として堆積させた。
その後、負極材料部、固体電解質材料部、正極材料部（ＬｉＩｎ箔）をあわせて、プレスを行わずに、１次組立体を得た。
得られた１次組立体を０．４Ｎｍのトルクでネジ締めすることにより、積層方向に７ＭＰａの拘束圧を印加し、電極部材を得た。結果を表１に示す。なお、比較例５で得られた電極部材の負極の切断面のＳｉ粒子同士の接着は、通電できなかったため、比較例３〜４と同様にＳＥＭ画像を確認せずに「×」と判断した。
(Comparative Example 5)
1. First, 150 mg of the solid electrolyte A powder was added to a cylinder made of PET and pressed at 3.5 ton / cm 2 (≈343 MPa) to form a solid electrolyte material part.
2. As the positive electrode active material of the all-solid-state battery, LiIn foil in which Li foil (manufactured by Honjo Chemical Co., Ltd.) was attached to In foil (manufactured by Nilaco Corporation, φ10 mm, thickness 0.1 mm) was used. The LiIn foil is disposed on one surface of the solid electrolyte material part, and subsequently, a powder of Si alone (an average particle size of 100 nm manufactured by Alfa aesar) as a negative electrode active material is applied to the other surface of the solid electrolyte material part. The deposition amount per unit area was 0.9 mg / cm 2 .
Thereafter, the negative electrode material part, the solid electrolyte material part, and the positive electrode material part (LiIn foil) were combined to obtain a primary assembly without performing pressing.
By screwing the obtained primary assembly with a torque of 0.4 Nm, a restraining pressure of 7 MPa was applied in the stacking direction to obtain an electrode member. The results are shown in Table 1. In addition, since adhesion between Si particles on the cut surface of the negative electrode of the electrode member obtained in Comparative Example 5 could not be energized, it was determined as “x” without confirming the SEM image as in Comparative Examples 3 to 4. .
１ 固体電解質材料部（固体電解質材料層）
１’ 固体電解質粉末
２ 負極材料部（負極材料層）
２’ 負極材料粉末（負極用合材）
３ 正極材料部（正極材料層）
３’ 正極材料粉末（正極用合材）
４ 固体電解質層
５ 負極
６ 正極
７ 他の部材
１０１ １次組立体
１０２ 全固体電池用電極部材
１０３ 全固体電池
1 Solid electrolyte material part (solid electrolyte material layer)
1 'solid electrolyte powder 2 negative electrode material part (negative electrode material layer)
2 'Negative electrode material powder (mixture for negative electrode)
3 Positive electrode material part (positive electrode material layer)
3 'Positive electrode material powder (mixture for positive electrode)
4 Solid Electrolyte Layer 5 Negative Electrode 6 Positive Electrode 7 Other Member 101 Primary Assembly 102 Electrode Member for All Solid Battery 103 All Solid Battery
Claims (1)
Ｌｉを含有する正極活物質を含む正極材料部、負極活物質としてＳｉ単体粉末を含み且つ結着材及び固体電解質を含まない負極材料部、並びに、前記正極材料部と前記負極材料部の間に配置された固体電解質材料部を備えた１次組立体を準備する準備工程、並びに、
前記１次組立体に、前記正極材料部、前記固体電解質材料部及び前記負極材料部の配列方向に１００ＭＰａ以上の拘束圧を印加した状態で、前記正極材料部側から前記固体電解質材料部を経由して前記負極材料部側に至る方向へ、負極材料部に含まれるＳｉ単体粉末１ｇ当たり９１０ｍＡｈ以上の電気量となるように通電し、前記負極材料部にＬｉイオンを挿入する通電工程を有する、全固体電池用電極部材の製造方法。 A method for producing an electrode member for an all-solid battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode,
A positive electrode material portion containing a positive electrode active material containing Li, a negative electrode material portion containing Si simple powder as a negative electrode active material and not containing a binder and a solid electrolyte, and between the positive electrode material portion and the negative electrode material portion A preparatory step of preparing a primary assembly with a disposed solid electrolyte material portion, and
The primary assembly is passed through the solid electrolyte material portion from the positive electrode material portion side in a state where a binding pressure of 100 MPa or more is applied to the primary assembly in the arrangement direction of the positive electrode material portion, the solid electrolyte material portion, and the negative electrode material portion. Then, in the direction to reach the negative electrode material part side, it has an energization step of energizing so that the amount of electricity is 910 mAh or more per 1 g of Si simple substance powder contained in the negative electrode material part, and inserting Li ions into the negative electrode material part. Manufacturing method of electrode member for all-solid-state battery.
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