JP2022011986A - Positive electrode active substance material for solid electrolyte-containing battery, and solid electrolyte-containing battery - Google Patents
Positive electrode active substance material for solid electrolyte-containing battery, and solid electrolyte-containing battery Download PDFInfo
- Publication number
- JP2022011986A JP2022011986A JP2020113446A JP2020113446A JP2022011986A JP 2022011986 A JP2022011986 A JP 2022011986A JP 2020113446 A JP2020113446 A JP 2020113446A JP 2020113446 A JP2020113446 A JP 2020113446A JP 2022011986 A JP2022011986 A JP 2022011986A
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- JP
- Japan
- Prior art keywords
- solid electrolyte
- positive electrode
- electrode active
- active material
- battery
- Prior art date
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 132
- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000013543 active substance Substances 0.000 title abstract 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002131 composite material Substances 0.000 claims abstract description 69
- 229940074371 monofluorophosphate Drugs 0.000 claims abstract description 11
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims abstract description 10
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- -1 fluorophosphoric acid compound Chemical class 0.000 claims description 60
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- 239000000203 mixture Substances 0.000 claims description 6
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- 239000011149 active material Substances 0.000 claims description 4
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- 239000010410 layer Substances 0.000 description 132
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- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229960004711 sodium monofluorophosphate Drugs 0.000 description 1
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本開示は、固体電解質含有電池用正極活物質材料及び固体電解質含有電池に関する。 The present disclosure relates to a positive electrode active material for a solid electrolyte-containing battery and a solid electrolyte-containing battery.
近年、パソコン、携帯電話等の情報関連機器、通信機器等の普及に伴い、その電源として利用される電池の需要が拡大している。電池の中でも、リチウムイオン二次電池は、起電力及びエネルギー密度が高いことから、携帯用電子機器等の用途に広く用いられている。従来のリチウムイオン二次電池には、イオンを移動させる媒体として、可燃性有機溶媒を含む液体の電解質（電解液）が使用されているが、このような電解液を用いた電池では、電解液の漏液、発火、爆発等を生ずる虞がある。
そこで、上記問題を解決すべく、安全性の高い電池として、固体電解質を使用し、可燃性有機溶媒の使用量を低減した電池の開発が進められている。特に、電解液を使用せず、電池を全固体化した全固体電池は、安全装置の簡素化が図れ、製造コストや生産性に優れると考えられている。
しかしながら、固体電解質を使用した電池を実用化するためには、充放電効率、容量、出力等の電池特性の改良が求められており、そのための開発が盛んに行われている。
In recent years, with the widespread use of information-related devices such as personal computers and mobile phones, communication devices, etc., the demand for batteries used as their power sources has been increasing. Among the batteries, the lithium ion secondary battery is widely used for applications such as portable electronic devices because of its high electromotive force and energy density. In conventional lithium ion secondary batteries, a liquid electrolyte (electrolyte solution) containing a flammable organic solvent is used as a medium for moving ions, but in a battery using such an electrolytic solution, an electrolytic solution is used. There is a risk of liquid leakage, ignition, explosion, etc.
Therefore, in order to solve the above problems, a battery using a solid electrolyte as a highly safe battery and reducing the amount of flammable organic solvent used is being developed. In particular, an all-solid-state battery in which the battery is completely solidified without using an electrolytic solution is considered to be excellent in manufacturing cost and productivity because the safety device can be simplified.
However, in order to put a battery using a solid electrolyte into practical use, improvement of battery characteristics such as charge / discharge efficiency, capacity, and output is required, and development for that purpose is being actively carried out.
例えば、特許文献１及び２には、リチウムとニオブの酸化物からなる被覆層で覆われたリチウム複合酸化物粒子を正極活物質として用いることで、電池容量及びサイクル特性を向上させる技術が開示されている。
また、特許文献３及び４には、Ｌｉ３ＰＯ４、ＬｉＮｂＯ３等のリチウムイオン伝導体；酸化物；酸窒化物；ハロゲン化合物；硫化物；リン化合物；等からなる被膜で覆われたリチウム複合酸化物を正極活物質として用いることで、初期容量を向上する技術が記載されている。
For example, Patent Documents 1 and 2 disclose techniques for improving battery capacity and cycle characteristics by using lithium composite oxide particles covered with a coating layer composed of an oxide of lithium and niobium as a positive electrode active material. ing.
Further, in Patent Documents 3 and 4, a lithium ion conductor such as Li 3 PO 4 and LiNbO 3 ; an oxide; an oxynitride; a halogen compound; a sulfide; a phosphorus compound; and the like are covered with a coating film. A technique for improving the initial capacity by using an oxide as a positive electrode active material is described.
特許文献１及び２では、ＬｉＮｂＯ３ターゲットを使用した出力３００～７００Ｗ条件下でのバレルスパッタリング法により被覆層を形成しており、特許文献３及び４では、原子層堆積法により被膜を形成している。バレルスパッタリング法及び原子層堆積法は、いずれも真空プロセスであるため、設備コストが高い、製造時のエネルギー消費量が多い、作業が煩雑である等の問題があり、量産化には不向きである。そこで、電池特性を向上させることのできる量産化可能な正極活物質材料の開発が求められている。また、特許文献１～４における正極活物質の被覆材料として用いられるリチウムとニオブの酸化物は、密度が高く、電池の軽量化を阻害する要因となっているため、より軽い被覆材料が求められている。 In Patent Documents 1 and 2, a coating layer is formed by a barrel sputtering method using a LiNbO 3 target under an output of 300 to 700 W, and in Patent Documents 3 and 4, a coating layer is formed by an atomic layer deposition method. There is. Since both the barrel sputtering method and the atomic layer deposition method are vacuum processes, they have problems such as high equipment cost, high energy consumption during manufacturing, and complicated work, and are not suitable for mass production. .. Therefore, there is a need to develop a mass-produceable positive electrode active material that can improve battery characteristics. Further, the oxides of lithium and niobium used as the coating material for the positive electrode active material in Patent Documents 1 to 4 have a high density and are a factor that hinders the weight reduction of the battery, so that a lighter coating material is required. ing.
本発明の課題は、従来よりも軽く、かつ、簡便、低コスト及び低エネルギーで製造することができ、さらに、固体電解質含有電池の容量、充放電効率等の電池特性を向上することのできる正極活物質材料を提供することである。 The subject of the present invention is a positive electrode that is lighter than conventional, can be manufactured easily, at low cost, and has low energy, and can further improve battery characteristics such as capacity and charge / discharge efficiency of a solid electrolyte-containing battery. It is to provide active material material.
本発明者は、上記課題を解決すべく検討を重ねた結果、正極活物質であるリチウム複合酸化物とフルオロリン酸化合物とを特定の割合で含有することにより上記課題を解決できることを見出し、本発明に至った。すなわち、本発明は以下を要旨とする。 As a result of repeated studies to solve the above problems, the present inventor has found that the above problems can be solved by containing a lithium composite oxide as a positive electrode active material and a fluorophosphoric acid compound in a specific ratio. It led to the invention. That is, the gist of the present invention is as follows.
［１］
リチウム複合酸化物と、
モノフルオロリン酸、ジフルオロリン酸及びそれらの塩からなる群より選択される１種以上のフルオロリン酸化合物と、
を含有し、
前記フルオロリン酸化合物の含有量が、前記リチウム複合酸化物１００質量部に対して０．０１質量部以上５．０質量部以下である、固体電解質含有電池用正極活物質材料。
［２］
前記フルオロリン酸化合物が、ジフルオロリン酸アルカリ金属塩である、［１］に記載の固体電解質含有電池用正極活物質材料。
［３］
前記フルオロリン酸化合物の含有量が、前記リチウム複合酸化物１００質量部に対して０．０１質量部以上２．０質量部以下である、［１］又は［２］に記載の固体電解質含有電池用正極活物質材料。
［４］
前記リチウム複合酸化物が、ＬｉａＮｉｂＭｎｃＣｏｄＡｅＯｆ（Ａは、Ｌｉ、Ｎｉ、Ｍｎ及びＣｏ以外の元素であり；ａ～ｆは、０．８≦ａ≦１．２、０≦ｂ≦０．９５、０≦ｃ≦０．５、０≦ｄ≦１．０、０．７≦ｂ＋ｃ＋ｄ≦１．１、０≦ｅ≦０．１及び１．８≦ｆ≦２．２を満たす。）で表される組成を有する、［１］～［３］のいずれかに記載の固体電解質含有電池用正極活物質材料。
［５］
前記リチウム複合酸化物が、前記フルオロリン酸化合物で被覆されている、［１］～［４］のいずれかに記載の固体電解質含有電池用正極活物質材料。
［６］
正極層、固体電解質層及び負極層をこの順に有し、
前記正極層又は前記固体電解質層が、モノフルオロリン酸、ジフルオロリン酸及びそれらの塩からなる群より選択される１種以上のフルオロリン酸化合物を含む、固体電解質含有電池。
［７］
前記固体電解質層が、硫化物固体電解質を含有する、［６］に記載の固体電解質含有電池。
［８］
前記正極層が、リチウム複合酸化物を含む、［６］又は［７］に記載の固体電解質含有電池。
[1]
Lithium composite oxide and
One or more fluorophosphate compounds selected from the group consisting of monofluorophosphate, difluorophosphate and salts thereof, and
Contains,
A positive electrode active material for a solid electrolyte-containing battery, wherein the content of the fluorophosphoric acid compound is 0.01 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the lithium composite oxide.
[2]
The positive electrode active material for a battery containing a solid electrolyte according to [1], wherein the fluorophosphoric acid compound is a difluorophosphoric acid alkali metal salt.
[3]
The solid electrolyte-containing battery according to [1] or [2], wherein the content of the fluorophosphoric acid compound is 0.01 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the lithium composite oxide. For positive electrode active material material.
[4]
The lithium composite oxide is Li a Ni b Mn c Co d A e Of (A is an element other than Li, Ni, Mn and Co; a to f are 0.8 ≦ a ≦ 1.2. , 0 ≦ b ≦ 0.95, 0 ≦ c ≦ 0.5, 0 ≦ d ≦ 1.0, 0.7 ≦ b + c + d ≦ 1.1, 0 ≦ e ≦ 0.1 and 1.8 ≦ f ≦ 2 The positive electrode active material for a battery containing a solid electrolyte according to any one of [1] to [3], which has the composition represented by (2).
[5]
The positive electrode active material for a battery containing a solid electrolyte according to any one of [1] to [4], wherein the lithium composite oxide is coated with the fluorophosphoric acid compound.
[6]
It has a positive electrode layer, a solid electrolyte layer, and a negative electrode layer in this order.
A solid electrolyte-containing battery in which the positive electrode layer or the solid electrolyte layer contains one or more fluorophosphate compounds selected from the group consisting of monofluorophosphate, difluorophosphate and salts thereof.
[7]
The solid electrolyte-containing battery according to [6], wherein the solid electrolyte layer contains a sulfide solid electrolyte.
[8]
The solid electrolyte-containing battery according to [6] or [7], wherein the positive electrode layer contains a lithium composite oxide.
本発明によれば、従来よりも軽く、かつ、簡便、低コスト及び低エネルギーで製造することができ、さらに、固体電解質含有電池の容量、充放電効率等の電池特性を向上することのできる正極活物質材料を提供することができる。 According to the present invention, a positive electrode that is lighter than conventional, can be manufactured easily, at low cost, and has low energy, and can improve battery characteristics such as capacity and charge / discharge efficiency of a solid electrolyte-containing battery. Active material materials can be provided.
以下に本発明の実施の形態を詳細に説明する。以下に記載する構成要件の説明は、本発明の実施態様の一例（代表例）であり、本発明はその要旨を超えない限り、これらの内容に特定はされない。 Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not specified in these contents unless the gist thereof is exceeded.
１．正極活物質材料
本発明の第１の実施形態は、リチウム複合酸化物と、モノフルオロリン酸、ジフルオロリン酸及びそれらの塩からなる群より選択される１種以上のフルオロリン酸化合物とを含有し、前記フルオロリン酸化合物の含有量が、前記リチウム複合酸化物１００質量部に対して０．０１質量部以上５．０質量部以下である固体電解質含有電池用正極活物質材料である。
1. 1. Positive Positive Material Active Material The first embodiment of the present invention contains a lithium composite oxide and one or more fluorophosphoric acid compounds selected from the group consisting of monofluorophosphoric acid, difluorophosphoric acid and salts thereof. The positive electrode active material for a solid electrolyte-containing battery, wherein the content of the fluorophosphoric acid compound is 0.01 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the lithium composite oxide.
１－１．リチウム複合酸化物
本実施形態では、正極活物質としてリチウム複合酸化物を使用する。リチウム複合酸化物としては、金属イオンを吸蔵及び放出し得るものであれば特に制限されず、例えばＮｉ、Ｍｎ及びＣｏからなる群より選択される１種以上の元素を含有するリチウム複合酸化物が挙げられる。このようなリチウム複合酸化物としては、式（Ｉ）で表される組成を有するリチウム複合酸化物が好適に例示される。
ＬｉａＮｉｂＭｎｃＣｏｄＡｅＯｆ （Ｉ）
1-1. Lithium Composite Oxide In this embodiment, a lithium composite oxide is used as the positive electrode active material. The lithium composite oxide is not particularly limited as long as it can occlude and release metal ions, and for example, a lithium composite oxide containing one or more elements selected from the group consisting of Ni, Mn and Co can be used. Can be mentioned. As such a lithium composite oxide, a lithium composite oxide having a composition represented by the formula (I) is preferably exemplified.
Li a Ni b Mn c Cod A e Of (I)
式中、Ａは、Ｌｉ、Ｎｉ、Ｍｎ及びＣｏ以外の元素を表す。より具体的には、Ａは、Ａｌ、Ｔｉ、Ｓｉ、Ｂｉ、Ｚｒ、Ｂ、Ｓｂ、Ｍｇ、Ｗ、Ｍｏ及びＣｒから選択される１種以上の元素を表す。これらのうち、Ａは、リチウム複合酸化物の表面変性を原因とする劣化抑制の観点から、Ａｌ、Ｚｒ、Ｂ、Ｓｂ及びＷから選択される１種以上の元素であることが好ましく、リチウム複合酸化物の低コスト化の観点からは、Ａｌ、Ｔｉ、Ｓｉ、Ｂ及びＭｇから選択される１種以上の元素であることが好ましい。
ａは、通常０．８以上、好ましくは０．９以上、より好ましくは０．９５以上、また、通常１．２以下、好ましくは１．１５以下、より好ましくは１．１以下である。
ｂは、通常０以上、好ましくは０．２以上、より好ましくは０．３以上、また、通常０．９５以下、好ましくは０．８以下、より好ましくは０．６以下である。
ｃは、通常０以上、好ましくは０．２以上、より好ましくは０．３以上、また、通常０．５以下、好ましくは０．４以下、より好ましくは０．３５以下である。
ｄは、通常０以上、好ましくは０．１５以上、より好ましくは０．３以上、また、通常１．０以下、好ましくは０．９以下、より好ましくは０．８以下である。
ｅは、通常０以上、好ましくは０．０３以上、より好ましくは０．０５以上、また、通常０．１以下、好ましくは０．０８以下、より好ましくは０．０６以下である。
ｆは、通常１．８以上、好ましくは１．９以上、より好ましくは１．９５以上、また、通常２．２以下、好ましくは２．１以下、より好ましくは２．０５以下である。
また、ｂ＋ｃ＋ｄは、通常０．７以上、好ましくは０．８以上、より好ましくは０．９以上、また、通常１．１以下、好ましくは１．０７以下、より好ましくは１．０５以下である。
ａ～ｆが上記範囲内であることにより、固体電解質含有電池の容量及び耐久性を向上し得る正極活物質材料が得られる。
In the formula, A represents an element other than Li, Ni, Mn and Co. More specifically, A represents one or more elements selected from Al, Ti, Si, Bi, Zr, B, Sb, Mg, W, Mo and Cr. Of these, A is preferably one or more elements selected from Al, Zr, B, Sb and W from the viewpoint of suppressing deterioration caused by surface modification of the lithium composite oxide, and is preferably a lithium composite. From the viewpoint of reducing the cost of the oxide, it is preferable that it is one or more elements selected from Al, Ti, Si, B and Mg.
a is usually 0.8 or more, preferably 0.9 or more, more preferably 0.95 or more, and usually 1.2 or less, preferably 1.15 or less, more preferably 1.1 or less.
b is usually 0 or more, preferably 0.2 or more, more preferably 0.3 or more, and usually 0.95 or less, preferably 0.8 or less, more preferably 0.6 or less.
c is usually 0 or more, preferably 0.2 or more, more preferably 0.3 or more, and usually 0.5 or less, preferably 0.4 or less, more preferably 0.35 or less.
d is usually 0 or more, preferably 0.15 or more, more preferably 0.3 or more, and usually 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less.
e is usually 0 or more, preferably 0.03 or more, more preferably 0.05 or more, and usually 0.1 or less, preferably 0.08 or less, more preferably 0.06 or less.
f is usually 1.8 or more, preferably 1.9 or more, more preferably 1.95 or more, and usually 2.2 or less, preferably 2.1 or less, more preferably 2.05 or less.
Further, b + c + d is usually 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and usually 1.1 or less, preferably 1.07 or less, more preferably 1.05 or less. ..
When a to f are within the above ranges, a positive electrode active material that can improve the capacity and durability of the solid electrolyte-containing battery can be obtained.
このようなリチウム複合酸化物としては、具体的には、層状リチウム複合酸化物であるＬｉＮｉＯ２、ＬｉＭｎＯ２、ＬｉＣｏＯ２、ＬｉＣｏ０．３３Ｎｉ０．３３Ｍｎ０．３３Ｏ２、ＬｉＣｏ０．３Ｎｉ０．５Ｍｎ０．２Ｏ２、ＬｉＣｏ０．２Ｎｉ０．６Ｍｎ０．２Ｏ２、ＬｉＣｏ０．１Ｎｉ０．８Ｍｎ０．１Ｏ２、ＬｉＣｏ０．１５Ｎｉ０．８Ａｌ０．０５Ｏ２等が挙げられ、ＬｉＣｏ０．３３Ｎｉ０．３３Ｍｎ０．３３Ｏ２が好ましい。 Specific examples of such a lithium composite oxide include LiNiO 2 , LiMnO 2 , LiCoO 2 , LiCo 0.33 Ni 0.33 Mn 0.33 O 2 , and LiCo 0.3 , which are layered lithium composite oxides. Ni 0.5 Mn 0.2 O 2 , LiCo 0.2 Ni 0.6 Mn 0.2 O 2 , LiCo 0.1 Ni 0.8 Mn 0.1 O 2 , LiCo 0.15 Ni 0.8 Al Examples thereof include 0.05 O 2 , and LiCo 0.33 Ni 0.33 Mn 0.33 O 2 is preferable.
リチウム複合酸化物の形状は、特に制限されないが、粒子であることが好ましく、真球状又は楕円上の粒子であることがより好ましい。リチウム複合酸化物の形状が粒子である場合、そのメジアン径（Ｄ５０）は、特に制限されないが、通常１μｍ以上、好ましくは３μｍ以上、より好ましくは５μｍ以上、また、通常２０μｍ以下、好ましくは１５μｍ
以下、より好ましくは１２μｍ以下である。上記メジアン径（Ｄ５０）は、レーザ回折・散乱法により求めることができる。
なお、リチウム複合酸化物の表面に後述する被覆層が形成されている場合、当該被覆層の厚さはナノメートルオーダーであって、リチウム複合酸化物のメジアン径（Ｄ５０）に対して非常に小さいため、マイクロメートルオーダーで規定するリチウム複合酸化物のメジアン径（Ｄ５０）と正極活物質材料のメジアン径（Ｄ５０）とは同一であるものとして扱うことができる。
The shape of the lithium composite oxide is not particularly limited, but is preferably particles, and more preferably spherical or elliptical particles. When the shape of the lithium composite oxide is a particle, its median diameter (D 50 ) is not particularly limited, but is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and usually 20 μm or less, preferably 15 μm.
Below, it is more preferably 12 μm or less. The median diameter (D 50 ) can be determined by a laser diffraction / scattering method.
When a coating layer described later is formed on the surface of the lithium composite oxide, the thickness of the coating layer is on the nanometer order, which is very small with respect to the median diameter ( D50 ) of the lithium composite oxide. Since it is small, it can be treated that the median diameter (D 50 ) of the lithium composite oxide specified on the order of nanometers and the median diameter (D 50 ) of the positive electrode active material material are the same.
１－２．フルオロリン酸化合物
本実施形態におけるフルオロリン酸化合物は、モノフルオロリン酸、ジフルオロリン酸及びそれらの塩からなる群より選択される１種以上の化合物である。モノフルオロリン酸及びジフルオロリン酸は、それぞれ、分子内に少なくとも１つのモノフルオロリン酸構造及びジフルオロリン酸構造を有する化合物であれば、特に制限されない。フルオロリン酸化合物は、１種単独で使用してもよく、２種以上を任意の組み合わせ及び比率で使用してもよい。なお、フルオロリン酸化合物には、固体電解質含有電池内で生成したものを含む。
1-2. Fluorophosphoric acid compound The fluorophosphoric acid compound in the present embodiment is one or more compounds selected from the group consisting of monofluorophosphoric acid, difluorophosphoric acid and salts thereof. The monofluorophosphate and the difluorophosphate are not particularly limited as long as they are compounds having at least one monofluorophosphate structure and a difluorophosphate structure in the molecule, respectively. The fluorophosphoric acid compound may be used alone or in any combination and ratio of two or more. The fluorophosphoric acid compound includes those produced in a solid electrolyte-containing battery.
フルオロリン酸化合物は、モノフルオロリン酸塩及びジフルオロリン酸塩から選択される化合物であることが好ましい。
フルオロリン酸化合物がモノフルオロリン酸又はジフルオロリン酸の塩である場合、当該塩のカウンターカチオンは、特に制限されず、リチウム、ナトリウム、カリウム等のアルカリ金属のカチオン；マグネシウム、カルシウム等アルカリ土類金属のカチオン；［ＮＲ１２１Ｒ１２２Ｒ１２３Ｒ１２４］＋（式中、Ｒ１２１～Ｒ１２４は、それぞれ独立して、水素原子又は炭素数１以上１２以下の有機基を表す。）で表されるアンモニウムカチオン；等が挙げられる。上記アンモニウムカチオンにおいて、Ｒ１２１～Ｒ１２４で表わされる炭素数１以上１２以下の有機基は特に制限されず、例えば、フッ素原子で置換されていてもよいアルキル基、ハロゲン原子又はアルキル基で置換されていてもよいシクロアルキル基、ハロゲン原子又はアルキル基で置換されていてもよいアリール基、置換基を有していてもよい窒素原子含有複素環基等が挙げられる。これらのうち、Ｒ１２１～Ｒ１２４は、独立して、水素原子、アルキル基、シクロアルキル基又は窒素原子含有複素環基等であることが好ましい。上記カウンターカチオンとしては、リチウム、ナトリウム、カリウム等のアルカリ金属のカチオンが好ましく、なかでもリチウムカチオンが好ましい。
The fluorophosphate compound is preferably a compound selected from monofluorophosphate and difluorophosphate.
When the fluorophosphate compound is a salt of monofluorophosphate or difluorophosphate, the counter cation of the salt is not particularly limited, and the cation of an alkali metal such as lithium, sodium and potassium; alkaline earth such as magnesium and calcium. Metallic cation; [NR 121 R 122 R 123 R 124 ] + (In the formula, R 121 to R 124 each independently represent a hydrogen atom or an organic group having 1 or more and 12 or less carbon atoms). Alkaline cation; etc. In the above ammonium cation, the organic group represented by R 121 to R 124 having 1 or more and 12 or less carbon atoms is not particularly limited, and is, for example, substituted with an alkyl group, a halogen atom or an alkyl group which may be substituted with a fluorine atom. Examples thereof include a cycloalkyl group which may be present, an aryl group which may be substituted with a halogen atom or an alkyl group, a nitrogen atom-containing heterocyclic group which may have a substituent, and the like. Of these, it is preferable that R 121 to R 124 are independently hydrogen atoms, alkyl groups, cycloalkyl groups, nitrogen atom-containing heterocyclic groups and the like. As the counter cation, alkali metal cations such as lithium, sodium and potassium are preferable, and among them, lithium cation is preferable.
具体的なモノフルオロリン酸塩及びジフルオロリン酸塩としては、モノフルオロリン酸リチウム、モノフルオロリン酸ナトリウム、モノフルオロリン酸カリウム、ジフルオロリン酸リチウム、ジフルオロリン酸ナトリウム、ジフルオロリン酸カリウム等のアルカリ金属塩が好ましく挙げられ、モノフルオロリン酸リチウム、ジフルオロリン酸リチウムがより好ましく、ジフルオロリン酸リチウムがさらに好ましい。 Specific examples of monofluorophosphate and difluorophosphate include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, lithium difluorophosphate, sodium difluorophosphate, potassium difluorophosphate and the like. Alkali metal salts are preferred, lithium monofluorophosphate and lithium difluorophosphate are more preferred, and lithium difluorophosphate is even more preferred.
本実施形態に係る正極活物質材料において、リチウム複合酸化物１００質量部に対するフルオロリン酸化合物の含有量は、通常０．０１質量部以上５．０質量部以下である。
固体電解質含有電池の大容量化の観点からは、フルオロリン酸化合物の含有量は、リチウム複合酸化物１００質量部に対して、好ましくは０．０３質量部以上、より好ましくは０．１質量部以上、さらに好ましくは０．２質量部以上、また、好ましくは２質量部以下、より好ましくは１質量部以下、さらに好ましくは０．８質量部以下である。
また、固体電解質含有電池の充放電効率向上の観点からは、フルオロリン酸化合物の含有量は、リチウム複合酸化物１００質量部に対して、好ましくは０．０３質量部以上、より好ましくは０．０５質量部以上、さらに好ましくは０．０８質量部以上、また、好ましくは２質量部以下、より好ましくは１質量部以下、さらに好ましくは０．５質量部以下である。
In the positive electrode active material of the present embodiment, the content of the fluorophosphoric acid compound with respect to 100 parts by mass of the lithium composite oxide is usually 0.01 parts by mass or more and 5.0 parts by mass or less.
From the viewpoint of increasing the capacity of the solid electrolyte-containing battery, the content of the fluorophosphate compound is preferably 0.03 part by mass or more, more preferably 0.1 part by mass with respect to 100 parts by mass of the lithium composite oxide. The above is more preferably 0.2 parts by mass or more, preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less.
Further, from the viewpoint of improving the charge / discharge efficiency of the solid electrolyte-containing battery, the content of the fluorophosphate compound is preferably 0.03 part by mass or more, more preferably 0. It is 05 parts by mass or more, more preferably 0.08 parts by mass or more, preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 parts by mass or less.
本実施形態に係る正極活物質材料において、リチウム複合酸化物とフルオロリン酸化合物とを含有していれば、含有の態様は特に制限されない。例えば、リチウム複合酸化物の表面にフルオロリン酸化合物が付着していてもよく、リチウム複合酸化物が空隙を有する場合には、当該空隙内にフルオロリン酸化合物が充填されていてもよく、好ましくは前者である。より具体的には、リチウム複合酸化物の表面の一部又は全部がフルオロリン酸化合物を含有する被覆層で覆われていることが好ましい。 As long as the positive electrode active material according to the present embodiment contains the lithium composite oxide and the fluorophosphoric acid compound, the mode of inclusion is not particularly limited. For example, the fluorophosphoric acid compound may be attached to the surface of the lithium composite oxide, and when the lithium composite oxide has voids, the voids may be filled with the fluorophosphoric acid compound, which is preferable. Is the former. More specifically, it is preferable that a part or all of the surface of the lithium composite oxide is covered with a coating layer containing a fluorophosphoric acid compound.
被覆層の厚さは、特に制限されないが、電池に適用した際に、正極活物質であるリチウム複合酸化物と固体電解質との反応を生じない程度の厚さであることが好ましい。具体的には、被覆層の厚さは、０．１ｎｍ以上、０．５ｎｍ以上又は２ｎｍ以上であってよく、また、１５ｎｍ以下、１０ｎｍ以下又は５ｎｍ以下であってよい。被覆層の厚さは、透過型電子顕微鏡（ＴＥＭ）画像解析により測定することができる。 The thickness of the coating layer is not particularly limited, but is preferably such that the lithium composite oxide, which is a positive electrode active material, does not react with the solid electrolyte when applied to a battery. Specifically, the thickness of the coating layer may be 0.1 nm or more, 0.5 nm or more or 2 nm or more, and may be 15 nm or less, 10 nm or less or 5 nm or less. The thickness of the coating layer can be measured by transmission electron microscope (TEM) image analysis.
また、被覆層は、固体電解質用電池の容量及び充放電効率向上の観点から、リチウム複合酸化物のより多くの面積を覆っていることが好ましく、リチウム複合酸化物の表面の全部を覆っていることがより好ましい。具体的には、リチウム複合酸化物の表面積全体に対する被覆層で覆われた表面の面積の比率（被覆率）は、好ましくは２０％以上、より好ましくは５０％以上、さらに好ましくは７０％以上である。なお、被覆率は、透過型電子顕微鏡（ＴＥＭ）画像解析により測定することができる。 Further, the coating layer preferably covers a larger area of the lithium composite oxide from the viewpoint of improving the capacity and charge / discharge efficiency of the solid electrolyte battery, and covers the entire surface of the lithium composite oxide. Is more preferable. Specifically, the ratio (coating ratio) of the area of the surface covered with the coating layer to the total surface area of the lithium composite oxide is preferably 20% or more, more preferably 50% or more, still more preferably 70% or more. be. The coverage can be measured by transmission electron microscope (TEM) image analysis.
フルオロリン酸化合物は、従来電池特性を向上させるために正極活物質に添加されてきたＬｉＮｂＯ３等の酸化物よりも密度が小さいため、電池の軽量化を阻害することなく電池容量、充放電効率等の電池特性の向上を実現し得る。従って、本実施形態に係る正極活物質材料は、スマートフォン、ノート型パソコン等の携帯用電子機器用電池の用途に特に有効である。 Since the fluorophosphate compound has a lower density than the oxide such as LiNbO3 which has been conventionally added to the positive electrode active material to improve the battery characteristics , the battery capacity and charge / discharge efficiency are not hindered from reducing the weight of the battery. It is possible to improve the battery characteristics such as. Therefore, the positive electrode active material according to the present embodiment is particularly effective for applications of batteries for portable electronic devices such as smartphones and notebook personal computers.
本発明者らは、正極活物質材料が正極活物質であるリチウム複合酸化物に加え、フルオロリン酸化合物を含有することにより電池容量、充放電効率等の電池特性が向上する理由について、以下のように推測している。
固体電解質含有電池では、固体電解質の形状が粒子であるため、固体電解質と正極活物質との接触面積が小さい。そのため、固体電解質と正極活物質との間の金属イオンの移動が制限され、高い電池特性が得られないところ、固体電解質及び正極活物質よりも柔軟性の高いフルオロリン酸化合物を正極活物質材料に含有させることにより、電池内で固体電解質と正極活物質との接触を維持しやすくなる。また、フルオロリン酸化合物自体も、金属イオンを通す材料であるため、固体電解質と正極活物質との間の金属イオンの移動を促進し、さらにはその状態を維持することができる。これにより、電池容量、充放電効率等の電池特性が向上すると考えられる。
The present inventors explain the reason why the battery characteristics such as battery capacity and charge / discharge efficiency are improved by containing a fluorophosphate compound in addition to the lithium composite oxide which is the positive electrode active material as the positive electrode active material. I'm guessing.
In the solid electrolyte-containing battery, since the shape of the solid electrolyte is particles, the contact area between the solid electrolyte and the positive electrode active material is small. Therefore, the movement of metal ions between the solid electrolyte and the positive electrode active material is restricted, and high battery characteristics cannot be obtained. Therefore, a fluorophosphate compound having higher flexibility than the solid electrolyte and the positive electrode active material is used as the positive electrode active material. By containing it in the battery, it becomes easy to maintain the contact between the solid electrolyte and the positive electrode active material in the battery. Further, since the fluorophosphate compound itself is also a material that allows metal ions to pass through, it is possible to promote the movement of metal ions between the solid electrolyte and the positive electrode active material, and to maintain that state. This is considered to improve battery characteristics such as battery capacity and charge / discharge efficiency.
また、電池に高電位の電圧が印加されると、正極活物質と固体電解質との接触界面に高抵抗層が形成されることが知られている。従って、正極活物質であるリチウム複合酸化物の表面上にフルオロリン酸化合物を付着させることにより、好ましくはリチウム複合酸化物がフルオロリン酸化合物で被覆されることにより、高抵抗層の形成を抑制し、固体電解質と正極活物質との間のイオン伝導性を確保できると考えられる。固体電解質含有電池の固体電解質として硫化物固体電解質を用いる場合、高抵抗層の形成が特に問題となるため、本実施形態に係る正極活物質材料は、硫化物固体電解質を含有する電池の電池特性向上に有効である。 Further, it is known that when a high potential voltage is applied to the battery, a high resistance layer is formed at the contact interface between the positive electrode active material and the solid electrolyte. Therefore, by adhering the fluorophosphoric acid compound on the surface of the lithium composite oxide which is the positive electrode active material, preferably, the lithium composite oxide is coated with the fluorophosphoric acid compound, thereby suppressing the formation of the high resistance layer. However, it is considered that the ionic conductivity between the solid electrolyte and the positive electrode active material can be ensured. When a sulfide solid electrolyte is used as the solid electrolyte of the solid electrolyte-containing battery, the formation of a high resistance layer becomes a particular problem. Therefore, the positive electrode active material according to the present embodiment has the battery characteristics of the battery containing the sulfide solid electrolyte. It is effective for improvement.
１－３．その他の成分
本実施形態に係る正極活物質材料は、リチウム複合酸化物及びフルオロリン酸化合物以
外に、本発明の効果を阻害しない範囲で、その他の成分を含有していてもよい。その他の成分としては、リチウム複合酸化物以外の公知の正極活物質、リチウムイオン伝導性を有する酸化物、導電材等が挙げられる。
1-3. Other Components The positive electrode active material according to the present embodiment may contain other components in addition to the lithium composite oxide and the fluorophosphoric acid compound as long as the effects of the present invention are not impaired. Examples of other components include known positive electrode active materials other than lithium composite oxides, oxides having lithium ion conductivity, conductive materials, and the like.
リチウム複合酸化物以外の公知の正極活物質としては、ＬｉＦｅＰＯ４、ＬｉＭｎＰＯ４、ＬｉＣｏＰＯ４、ＴｉＳ２、ＭｏＳ２、ＦｅＳ、ＦｅＳ２、ＣｕＳ、Ｎｉ３Ｓ２、Ｂｉ２Ｏ３、Ｂｉ２Ｐｂ２Ｏ５、ＣｕＯ、Ｖ６Ｏ１３等が挙げられる。
イオン伝導性酸化物としては、例えばＬｉ３ＰＯ４、Ｌｉ３ＢＯ３、Ｌｉ４ＳｉＯ４、ＬｉＮｂＯ３、ＬｉＴｉＯ３、Ｌｉ２ＺｒＯ３等が挙げられる。
また、導電材としては、例えば黒鉛、高配向性グラファイト、メソカーボンマイクロビーズ、アセチレンブラック、ケッチェンブラック、カーボンナノチューブ、カーボンナノファイバー等の炭素質材料；ニッケル、銅、鉄、チタン、インジウム、ケイ素、スズ、アルミニウム、ステンレス鋼（ＳＵＳ）等の金属；等が挙げられる。導電材の形状は特に制限されず、例えば粒子状、繊維状等の形状であってよい。
Known positive electrode active materials other than the lithium composite oxide include LiFePO 4 , LiMnPO 4 , LiCoPO 4 , TiS 2 , MoS 2 , FeS, FeS 2 , CuS, Ni 3 S 2 , Bi 2 O 3 , and Bi 2 Pb 2 . Examples thereof include O 5 , CuO, and V 6 O 13 .
Examples of the ion conductive oxide include Li 3 PO 4 , Li 3 BO 3 , Li 4 SiO 4 , LiNbO 3 , LiTIO 3 , Li 2 ZrO 3 and the like.
Examples of the conductive material include carbonaceous materials such as graphite, highly oriented graphite, mesocarbon microbeads, acetylene black, ketjen black, carbon nanotubes, and carbon nanofibers; nickel, copper, iron, titanium, indium, and silicon. , Metals such as tin, aluminum, stainless steel (SUS); and the like. The shape of the conductive material is not particularly limited, and may be, for example, a particle shape, a fibrous shape, or the like.
正極活物質材料におけるその他の成分の含有量は、リチウム複合酸化物１００質量部に対して通常１０質量部以下である。 The content of other components in the positive electrode active material is usually 10 parts by mass or less with respect to 100 parts by mass of the lithium composite oxide.
１－４．正極活物質材料の製造方法
本実施形態に係る正極活物質材料の製造方法は、リチウム複合酸化物、フルオロリン酸化合物及び必要に応じてその他の成分を特定比率で混合させることができる限り、特に限定されない。
簡便な製造方法としては、フルオロリン酸化合物を含有する塗布液をリチウム複合酸化物に塗布し、乾燥する方法が挙げられる。塗布の方法は特に制限されず、例えば後述する実施例で示すように、リチウム複合酸化物とフルオロリン酸化合物を含有する塗布液とを混合及び攪拌する方法が挙げられる。また、固体電解質含有電池の製造過程において、正極集電体上に配置されたリチウム複合酸化物にフルオロリン酸化合物を含有する塗布液を塗布し、乾燥する方法も挙げられる。リチウム複合酸化物が粒子状である場合には、転動流動式コーティング法、静電噴霧法等を採用でき、リチウム複合酸化物が薄膜状である場合には、ディップコーティング法、スピンコーティング法等を採用することもできる。これらうち、設備コスト及び製造時のエネルギー消費量を抑制する観点、並びにリチウム複合酸化物がフルオロリン酸化合物で被覆された正極活物質材料を容易に製造できる観点から、リチウム複合酸化物とフルオロリン酸化合物を含有する塗布液とを混合及び攪拌する方法が好ましい。
1-4. Method for Producing Positive Electrode Active Material The method for producing a positive electrode active material according to the present embodiment is particularly limited as long as a lithium composite oxide, a fluorophosphoric acid compound and, if necessary, other components can be mixed in a specific ratio. Not limited.
As a simple production method, a method of applying a coating liquid containing a fluorophosphoric acid compound to a lithium composite oxide and drying it can be mentioned. The coating method is not particularly limited, and examples thereof include a method of mixing and stirring a coating liquid containing a lithium composite oxide and a fluorophosphoric acid compound, as shown in Examples described later. Further, in the process of manufacturing the solid electrolyte-containing battery, there is also a method of applying a coating liquid containing a fluorophosphoric acid compound to a lithium composite oxide arranged on a positive electrode current collector and drying it. When the lithium composite oxide is in the form of particles, a rolling flow coating method, an electrostatic spraying method, etc. can be adopted, and when the lithium composite oxide is in the form of a thin film, a dip coating method, a spin coating method, etc. can be adopted. Can also be adopted. Of these, lithium composite oxide and fluorophosphorus from the viewpoint of suppressing equipment cost and energy consumption during manufacturing, and from the viewpoint of easily manufacturing a positive electrode active material material in which the lithium composite oxide is coated with a fluorophosphoric acid compound. A method of mixing and stirring with a coating liquid containing an acid compound is preferable.
なお、正極活物質材料がその他の成分を含有する場合、その他の成分は上記フルオロリン酸化合物を含有する塗布液に配合され、フルオロリン酸化合物とともにリチウム複合酸化物に塗布してもよく、リチウム複合酸化物とともに塗布液を塗布されてもよい。 When the positive electrode active material contains other components, the other components may be blended in the coating liquid containing the fluorophosphoric acid compound and may be applied to the lithium composite oxide together with the fluorophosphoric acid compound, or lithium. The coating liquid may be applied together with the composite oxide.
上記フルオロリン酸化合物を含有する塗布液に用いる溶媒としては、上記フルオロリン酸化合物を溶解又は分散し得る限り特に制限されず、例えば、水；メタノール、エタノール、イソプロピルアルコール等のアルコール溶媒；ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、テトラヒドロフラン等のエーテル溶媒；蟻酸メチル、蟻酸エチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸フェニル等のエステル溶媒；ジメチルカーボネート、ジエチルカーボネート、プロピレンカーボネート等のカーボネート溶媒；ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、テトラクロロエタン等のハロゲン化炭化水素溶媒；アセトン、メチルエチルケトン、ジエチルケトン等のケトン溶媒；ヘキサン、シクロヘキサン、ベンゼン、トルエン、キシレン等の炭化水素系溶媒；アセトニトリル、プロピオニトリル等のニトリル溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等のアミド溶媒；等が挙
げられる。これらのうち、溶媒はフルオロリン酸化合物の溶解性又は分散性が高く、また、溶媒を揮発させる際のエネルギー消費量を抑制する点で、適度な揮発性を有するものが好ましい。具体的には、溶媒は、カーボネート溶媒であることが好ましい。なお、これらの溶媒は、１種単独で使用してもよく、２種以上を任意の組み合わせ及び比率で使用してもよい。
The solvent used for the coating liquid containing the fluorophosphate compound is not particularly limited as long as the fluorophosphate compound can be dissolved or dispersed, and is, for example, water; an alcohol solvent such as methanol, ethanol, isopropyl alcohol; diethyl ether. , Dipropyl ether, diisopropyl ether, ether solvent such as tetrahydrofuran; ester solvent such as methyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, phenyl acetate; carbonate solvent such as dimethyl carbonate, diethyl carbonate, propylene carbonate; dichloromethane. , Chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane and other halogenated hydrocarbon solvents; acetone, methyl ethyl ketone, diethyl ketone and other ketone solvents; hexane, cyclohexane, benzene, toluene, xylene and other hydrocarbon solvents; acetonitrile, propio A nitrile solvent such as nitrile; an amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; and the like can be mentioned. Of these, the solvent preferably has high solubility or dispersibility of the fluorophosphoric acid compound and has appropriate volatility in terms of suppressing energy consumption when volatilizing the solvent. Specifically, the solvent is preferably a carbonate solvent. In addition, these solvents may be used individually by 1 type, and 2 or more types may be used in arbitrary combinations and ratios.
乾燥方法は、前記溶媒を揮発により除去できる限り特に限定されない。乾燥に際しては、温度、圧力、攪拌等の各条件は、塗布液に用いた溶媒、塗布量等に応じて適宜選択することができる。 The drying method is not particularly limited as long as the solvent can be removed by volatilization. At the time of drying, each condition such as temperature, pressure and stirring can be appropriately selected according to the solvent used for the coating liquid, the coating amount and the like.
以上、正極活物質材料の簡便な製造方法について説明したが、スパッタリング法、静電噴霧法等の煩雑な手法によりフルオロリン酸化合物をリチウム複合酸化物に付着させることで正極活物質材料を製造した場合であっても、本発明の効果を発揮できる。
また、本実施形態に係る正極活物質材料には、後述する固体電解質含有電池の製造過程で生成したもの及び電池内で生成したものを含む。
The simple method for producing the positive electrode active material has been described above, but the positive electrode active material was produced by adhering the fluorophosphoric acid compound to the lithium composite oxide by a complicated method such as a sputtering method or an electrostatic spraying method. Even in this case, the effect of the present invention can be exhibited.
Further, the positive electrode active material material according to the present embodiment includes those produced in the manufacturing process of the solid electrolyte-containing battery described later and those produced in the battery.
２．固体電解質含有電池
本発明の第２の実施形態は、正極層、固体電解質層及び負極層をこの順に有し、前記正極層又は前記固体電解質層が、モノフルオロリン酸、ジフルオロリン酸及びそれらの塩からなる群より選択される１種以上のフルオロリン酸化合物を含む固体電解質含有電池である。
2. 2. Solid Electrolyte-Containing Battery The second embodiment of the present invention has a positive electrode layer, a solid electrolyte layer and a negative electrode layer in this order, and the positive electrode layer or the solid electrolyte layer is monofluorophosphate, difluorophosphate and their respective. A solid electrolyte-containing battery containing one or more fluorophosphate compounds selected from the group consisting of salts.
固体電解質含有電池中でのフルオロリン酸化合物の分布は特に制限されないが、正極層、正極層と固体電解質層との界面等に分布していることが好ましい。なかでも、フルオロリン酸化合物は、正極層に分布していることが好ましく、より具体的には、正極層中の正極活物質等の間に分布していることが好ましく、正極活物質の近傍に分布していることがより好ましく、正極活物質を被覆するように分布していることがさらに好ましい。 The distribution of the fluorophosphoric acid compound in the solid electrolyte-containing battery is not particularly limited, but it is preferably distributed in the positive electrode layer, the interface between the positive electrode layer and the solid electrolyte layer, and the like. Among them, the fluorophosphate compound is preferably distributed in the positive electrode layer, more specifically, distributed between the positive electrode active materials and the like in the positive electrode layer, and is in the vicinity of the positive electrode active material. It is more preferable that it is distributed in, and it is further preferable that it is distributed so as to cover the positive electrode active material.
本実施形態に係る固体電解質含有電池は、一次電池であってもよく、二次電池であってもよいが、二次電池であることが好ましい。繰り返し充放電でき、例えば車載用電池等として有用だからである。固体電解質含有電池の形状としては、例えば、コイン型、ラミネート型、円筒型、角型等が挙げられる。 The solid electrolyte-containing battery according to the present embodiment may be a primary battery or a secondary battery, but is preferably a secondary battery. This is because it can be repeatedly charged and discharged and is useful as, for example, an in-vehicle battery. Examples of the shape of the solid electrolyte-containing battery include a coin type, a laminated type, a cylindrical type, and a square type.
２－１．正極層
本発明における正極層は、金属イオンを吸蔵及び放出し得る正極活物質を含有する層であり、必要に応じて固体電解質、導電材、結着材等を含有していてもよい。
2-1. Positive Electrode Layer The positive electrode layer in the present invention is a layer containing a positive electrode active material that can occlude and release metal ions, and may contain a solid electrolyte, a conductive material, a binder, and the like, if necessary.
正極活物質としては、金属イオンを吸蔵及び放出し得る物質であれば特に制限されず、第１の実施形態に係る正極活物質材料における正極活物質（すなわち、リチウム複合酸化物及び必要に応じてリチウム複合酸化物以外の公知の正極活物質）、その他の公知の正極活物質等が挙げられる。これらのうち、正極活物質は、第１の実施形態に係る正極活物質材料において正極活物質として用いられるリチウム複合酸化物であることが好ましい。また、正極層は、第１の実施形態に係る正極活物質材料を用いて形成されたものであることが好ましい。正極活物質は、１種単独で使用してもよく、２種以上を任意の組み合わせ及び比率で使用してもよい。
正極層中、正極活物質の含有量は、好ましくは２０質量％以上であり、より好ましくは３０質量％以上、さらに好ましくは５０質量％以上、また、好ましくは９５質量％以下、より好ましくは９０質量％以下である。
The positive electrode active material is not particularly limited as long as it is a substance capable of storing and releasing metal ions, and the positive electrode active material in the positive electrode active material material according to the first embodiment (that is, a lithium composite oxide and, if necessary). Known positive electrode active materials other than lithium composite oxides), other known positive electrode active materials, and the like can be mentioned. Of these, the positive electrode active material is preferably a lithium composite oxide used as the positive electrode active material in the positive electrode active material material according to the first embodiment. Further, the positive electrode layer is preferably formed by using the positive electrode active material material according to the first embodiment. As the positive electrode active material, one type may be used alone, or two or more types may be used in any combination and ratio.
The content of the positive electrode active material in the positive electrode layer is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass. It is less than mass%.
固体電解質としては、後述する固体電解質層に含まれる固体電解質として例示されるも
のから適宜選択して用いることができ、固体電解質層に含まれる固体電解質と同一のものを用いることが好ましい。正極層に含まれる固体電解質の含有量は、電池の種類によって異なるもが、正極層中、好ましくは０．１体積％以上、より好ましくは１体積％以上、さらに好ましくは１０体積％以上、また、好ましくは８０体積％以下、より好ましくは６０体積％以下、さらに好ましくは５０体積％以下である。
導電材としては、黒鉛、高配向性グラファイト、メソカーボンマイクロビーズ、アセチレンブラック、ケッチェンブラック、カーボンナノチューブ、カーボンナノファイバー、気相法炭素繊維等の炭素質材料；ニッケル、銅、鉄、インジウム、ケイ素、スズ、チタン、アルミニウム、ステンレス鋼（ＳＵＳ）等の金属；等が挙げられる。正極層が導電材を含有することにより、正極層の導電性を向上させることができる。
結着材としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等のフッ素樹脂が挙げられる。
As the solid electrolyte, one can be appropriately selected and used from those exemplified as the solid electrolyte contained in the solid electrolyte layer described later, and it is preferable to use the same solid electrolyte as the solid electrolyte contained in the solid electrolyte layer. The content of the solid electrolyte contained in the positive electrode layer varies depending on the type of battery, but is preferably 0.1% by volume or more, more preferably 1% by volume or more, still more preferably 10% by volume or more, and more preferably 10% by volume or more in the positive electrode layer. It is preferably 80% by volume or less, more preferably 60% by volume or less, and further preferably 50% by volume or less.
As conductive materials, carbonaceous materials such as graphite, highly oriented graphite, mesocarbon microbeads, acetylene black, ketjen black, carbon nanotubes, carbon nanofibers, and vapor phase carbon fibers; nickel, copper, iron, indium, etc. Metals such as silicon, tin, titanium, aluminum and stainless steel (SUS); and the like. Since the positive electrode layer contains a conductive material, the conductivity of the positive electrode layer can be improved.
Examples of the binder include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF).
なお、正極層の厚さは、例えば０．１μｍ以上１０００μｍ以下の範囲内であることが好ましい。 The thickness of the positive electrode layer is preferably in the range of, for example, 0.1 μm or more and 1000 μm or less.
２－２．負極層
本発明における負極層は、金属イオンを吸蔵及び放出し得る負極活物質を含有する層であり、負極活物質の他に、必要に応じて固体電解質、導電材、結着材等を含有していてもよい。
2-2. Negative electrode layer The negative electrode layer in the present invention is a layer containing a negative electrode active material that can occlude and release metal ions, and contains a solid electrolyte, a conductive material, a binder, and the like, if necessary, in addition to the negative electrode active material. You may be doing it.
負極活物質としては、特に制限されず、公知の負極活物質を用いることができる。公知の負極活物質としては、天然黒鉛、人造黒鉛、非晶質炭素、炭素被覆黒鉛、黒鉛被覆黒鉛、樹脂被覆黒鉛等の炭素質材料；リチウム、リチウム合金、それらの酸化物、炭化物、窒化物、硫化物等の化合物等の金属材料；等が挙げられる。これらのうち、負極活物質は、金属材料であることが好ましく、Ｉｎ－Ｌｉ合金であることがより好ましい。
負極層中、負極活物質の含有量は、好ましくは３０質量％以上、より好ましくは５０質量％以上、また、好ましくは９５質量％以下、より好ましくは９０質量％以下である。
The negative electrode active material is not particularly limited, and a known negative electrode active material can be used. Known negative electrode active materials include carbonaceous materials such as natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, and resin-coated graphite; lithium, lithium alloys, their oxides, carbides, and nitrides. , Metallic materials such as compounds such as sulfide; and the like. Of these, the negative electrode active material is preferably a metal material, more preferably an In—Li alloy.
The content of the negative electrode active material in the negative electrode layer is preferably 30% by mass or more, more preferably 50% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less.
固体電解質としては、後述する固体電解質層に含まれる固体電解質として例示されるものから適宜選択して用いることができ、固体電解質層に含まれる固体電解質と同一のものを用いることが好ましい。負極層に含まれる固体電解質の含有量は、電池の種類によって異なるもが、負極層中、好ましくは０．１体積％以上、より好ましくは１体積％以上、さらに好ましくは１０体積％以上、また、好ましくは８０体積％以下、より好ましくは６０体積％以下、さらに好ましくは５０体積％以下である。
導電材としては、正極層に含まれていてもよい導電材と同様のものが挙げられる。負極層が導電材を含有することにより、負極層の導電性を向上させることができる。
結着材としては、スチレン－ブタジエンゴム（ＳＢＲ）、セルロース、ポリイミド等のポリマーが挙げられる。
As the solid electrolyte, one can be appropriately selected and used from those exemplified as the solid electrolyte contained in the solid electrolyte layer described later, and it is preferable to use the same solid electrolyte as the solid electrolyte contained in the solid electrolyte layer. The content of the solid electrolyte contained in the negative electrode layer varies depending on the type of battery, but is preferably 0.1% by volume or more, more preferably 1% by volume or more, still more preferably 10% by volume or more, and more preferably 10% by volume or more in the negative electrode layer. It is preferably 80% by volume or less, more preferably 60% by volume or less, and further preferably 50% by volume or less.
Examples of the conductive material include the same conductive materials that may be contained in the positive electrode layer. Since the negative electrode layer contains a conductive material, the conductivity of the negative electrode layer can be improved.
Examples of the binder include polymers such as styrene-butadiene rubber (SBR), cellulose, and polyimide.
なお、負極層の厚さは、例えば０．１μｍ以上１０００μｍ以下の範囲内であることが好ましい。 The thickness of the negative electrode layer is preferably in the range of, for example, 0.1 μm or more and 1000 μm or less.
２－３．固体電解質層
固体電解質層は、正極層と負極層との間に形成される層であり、固体電解質を含有する。固体電解質としては、イオンの伝導を行うことができれば特に制限されず、例えば硫化物固体電解質、酸化物固体電解質、水素化物固体電解質等が挙げられる。これらのうち、固体電解質は、イオン伝導性が高い点で、硫化物固体電解質であることが好ましい。固体電解質は、１種単独で使用してもよく、２種以上を任意の組み合わせ及び比率で使用してもよい。
2-3. Solid electrolyte layer The solid electrolyte layer is a layer formed between the positive electrode layer and the negative electrode layer, and contains a solid electrolyte. The solid electrolyte is not particularly limited as long as it can conduct ions, and examples thereof include a sulfide solid electrolyte, an oxide solid electrolyte, and a hydride solid electrolyte. Of these, the solid electrolyte is preferably a sulfide solid electrolyte in that it has high ionic conductivity. As the solid electrolyte, one type may be used alone, or two or more types may be used in any combination and ratio.
硫化物固体電解質としては、例えば、Ｌｉ３ＰＳ４、Ｌｉ２Ｓ－Ｐ２Ｓ５、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＬｉＩ、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＬｉＢｒ、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＬｉＣｌ、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ｌｉ２Ｏ、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ｌｉ２Ｏ－ＬｉＩ、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ｌｉ３Ｎ、Ｌｉ２Ｓ－ＳｉＳ２、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉＩ、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉＢｒ、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉＣｌ、Ｌｉ２Ｓ－ＳｉＳ２－Ｂ２Ｓ３－ＬｉＩ、Ｌｉ２Ｓ－ＳｉＳ２－Ｐ２Ｓ５－ＬｉＩ、Ｌｉ２Ｓ－Ｂ２Ｓ３、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＺｍＳｎ（ただし、ｍ、ｎは正の数を表し；Ｚは、Ｇｅ、Ｚｎ、Ｇａのいずれかの元素を表す。）、Ｌｉ２Ｓ－ＧｅＳ２、Ｌｉ２Ｓ－ＳｉＳ２－Ｌｉ３ＰＯ４、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉｐＭＯｑ（ただし、ｐ、ｑは正の数を表し；Ｍは、Ｐ、Ｓｉ、Ｇｅ、Ｂ、Ａｌ、Ｇａ、Ｉｎのいずれかの元素を表す。）、Ｌｉ１０ＧｅＰ２Ｓ１２等を挙げることができる。なお、上記「Ｌｉ２Ｓ－Ｐ２Ｓ５」の記載は、Ｌｉ２Ｓ及びＰ２Ｓ５を含む原料組成物を用いてなる硫化物固体電解質を意味し、他の記載についても同様である。これらのうち、硫化物固体電解質は、Ｌｉ３ＰＳ４であることが好ましい。 Examples of the sulfide solid electrolyte include Li 3 PS 4 , Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiI, Li 2 SP 2 S 5 -LiBr, Li 2 SP. 2 S 5 -LiCl, Li 2 SP 2 S 5 -Li 2 O, Li 2 SP 2 S 5 -Li 2 O-LiI, Li 2 SP 2 S 5 -Li 3 N, Li 2 S -SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -Li I, Li 2 SB 2 S 3 , Li 2 SP 2 S 5 -Z m Sn (where m and n represent positive numbers; Z is Ge, Zn. , Li 2 S-GeS 2 , Li 2 S-SiS 2 -Li 3 PO 4 , Li 2 S-SiS 2 -Li p MO q (where p and q are positive) Represents the number of; M represents any element of P, Si, Ge, B, Al, Ga, In), Li 10 GeP 2 S 12 and the like. The above description of "Li 2 SP 2 S 5" means a sulfide solid electrolyte using a raw material composition containing Li 2 S and P 2 S 5 , and the same applies to other descriptions. .. Of these, the sulfide solid electrolyte is preferably Li 3 PS 4 .
酸化物固体電解質としては、Ｌｉ１＋ｘＡｌｘＧｅ２－ｘ（ＰＯ４）３（０≦ｘ≦２）で表される化合物（ＬＡＧＰ）、Ｌｉ１＋ｘＡｌｘＴｉ２－ｘ（ＰＯ４）３（０≦ｘ≦２）で表される化合物（ＬＡＴＰ）等のＮＡＳＩＣＯＮ型構造を有する化合物；ＬｉＬａＴｉＯ（例えばＬｉ０．３４Ｌａ０．５１ＴｉＯ３）；ＬｉＰＯＮ（例えばＬｉ２．９ＰＯ３．３Ｎ０．４６）；ＬｉＬａＺｒＯ（例えばＬｉ７Ｌａ３Ｚｒ２Ｏ１２）；等が挙げられる。 Examples of the oxide solid electrolyte include a compound (LAGP) represented by Li 1 + x Al x Ge 2-x (PO 4 ) 3 (0 ≦ x ≦ 2), and Li 1 + x Al x Ti 2-x (PO 4 ) 3 (. A compound having a NASICON type structure such as a compound (LATP) represented by 0 ≦ x ≦ 2); LiLaTiO (for example, Li 0.34 La 0.51 TiO 3 ); LiPON (for example, Li 2.9 PO 3.3 N). 0.46 ); LiLaZrO (for example, Li 7 La 3 Zr 2 O 12 ); and the like.
水素化物固体電解質としては、ＬｉＢＨ４、ＬｉＢＨ４－３ＫＩ、ＬｉＢＨ４－ＰＩ２、ＬｉＢＨ４－Ｐ２Ｓ５、ＬｉＢＨ４－ＬｉＮＨ２、３ＬｉＢＨ４－ＬｉＩ、ＬｉＮＨ２、Ｌｉ２ＡｌＨ６、Ｌｉ（ＮＨ２）２Ｉ、Ｌｉ２ＮＨ、ＬｉＧｄ（ＢＨ４）３Ｃｌ、Ｌｉ２（ＢＨ４）（ＮＨ２）、Ｌｉ３（ＮＨ２）Ｉ、Ｌｉ４（ＢＨ４）（ＮＨ２）３等が挙げられる。 Examples of the borohydride solid electrolyte include LiBH 4 , LiBH 4-3KI, LiBH 4 -PI 2 , LiBH 4 -P 2 S 5 , LiBH 4 -LiNH 2 , 3LiBH 4 - LiI, LiNH 2 , Li 2 AlH 6 , Li ( NH 2 ) 2 I, Li 2 NH, LiGd (BH 4 ) 3 Cl, Li 2 (BH 4 ) (NH 2 ), Li 3 (NH 2 ) I, Li 4 (BH 4 ) (NH 2 ) 3 etc. Can be mentioned.
ポリマー系固体電解質として、ポリアルキレンオキシド、ポリシロキサン等の有機ポリマーが挙げられる。 Examples of the polymer-based solid electrolyte include organic polymers such as polyalkylene oxide and polysiloxane.
固体電解質層中、固体電解質の含有量は、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上である。 The content of the solid electrolyte in the solid electrolyte layer is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.
本実施形態における固体電解質層には、さらに非水系電解液、上記ポリマー系固体電解質に非水電解液を保持させたゲル状の電解質等の液状又はゲル状電解質を含んでいてもよい。
非水系電解液としては、特に制限されず、公知のものを用いることができる。公知の非水系電解液としては、特開２０２０－０６４８７３号公報、特開２０２０－０６４８２５号公報、特開２０２０－０３８８３４号公報、特開２０１９－１８６２２２号公報、特開２０１９－１３５７３０号公報等に記載の非水系電解液が挙げられる。
固体電解質層が液状又はゲル状電解質を含有する場合、該液状又はゲル状電解質の含有量は、好ましくは１０質量％以下、より好ましくは５質量％以下、さらに好ましくは３質量％以上である。
The solid electrolyte layer in the present embodiment may further contain a liquid or gel-like electrolyte such as a non-aqueous electrolyte solution and a gel-like electrolyte obtained by holding the non-aqueous electrolyte solution in the polymer-based solid electrolyte.
The non-aqueous electrolyte solution is not particularly limited, and known ones can be used. Examples of known non-aqueous electrolyte solutions include JP-A-2020-064873, JP-A-2020-664825, JP-A-2020-038834, JP-A-2019-186222, JP-A-2019-135730, and the like. Examples thereof include the non-aqueous electrolyte solution described.
When the solid electrolyte layer contains a liquid or gel-like electrolyte, the content of the liquid or gel-like electrolyte is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or more.
固体電解質層の厚さは、例えば０．１μｍ～１０００μｍの範囲内、中でも０．１μｍ～３００μｍの範囲内であることが好ましい。 The thickness of the solid electrolyte layer is preferably in the range of, for example, 0.1 μm to 1000 μm, particularly preferably in the range of 0.1 μm to 300 μm.
２－４．その他の構成
本実施形態に係る固体電解質含有電池は、上述した正極層、負極層及び固体電解質層を
有し、通常は、さらに正極層の集電を行う正極集電体及び負極層の集電を行う負極集電体を有する。正極集電体の材料としては、銅、ニッケル、鉄、チタン、アルミニウム、アルミニウム合金、ステンレス鋼（ＳＵＳ）等が挙げられ、好ましくはアルミニウムである。一方、負極集電体の材料としては、ステンレス鋼（ＳＵＳ）、銅、ニッケル、炭素等が挙げられ、好ましくは銅である。また、正極集電体及び負極集電体の厚さ及び形状は、電池の用途等に応じて適宜選択することができる。
2-4. Other Configurations The solid electrolyte-containing battery according to the present embodiment has the above-mentioned positive electrode layer, negative electrode layer, and solid electrolyte layer, and usually collects electricity from the positive electrode collector and the negative electrode layer, which further collects electricity from the positive electrode layer. Has a negative electrode current collector. Examples of the material of the positive electrode current collector include copper, nickel, iron, titanium, aluminum, aluminum alloy, stainless steel (SUS) and the like, and aluminum is preferable. On the other hand, examples of the material of the negative electrode current collector include stainless steel (SUS), copper, nickel, carbon and the like, and copper is preferable. Further, the thickness and shape of the positive electrode current collector and the negative electrode current collector can be appropriately selected according to the use of the battery and the like.
また、固体電解質含有電池に用いられる電池ケースとしては、一般的な電池ケースを用いることができる。一般的な電池ケースとしては、ステンレス鋼製電池ケース等が挙げられる。 Further, as the battery case used for the solid electrolyte-containing battery, a general battery case can be used. Examples of a general battery case include a stainless steel battery case.
２－５．固体電解質含有電池の製造方法
本実施形態に係る固体電解質含有電池の製造方法は、上述した固体電解質含有電池を得ることができる方法であれば、特に制限されないが、好適な製造方法としては、下記のものが挙げられる。
2-5. Method for Manufacturing a Solid Electrolyte-Containing Battery The method for manufacturing a solid electrolyte-containing battery according to the present embodiment is not particularly limited as long as it can obtain the above-mentioned solid electrolyte-containing battery, but the preferred manufacturing method is as follows. Can be mentioned.
（１ａ）第１の実施形態に係る正極活物質材料、溶媒、及び必要に応じて固体電解質、導電材、結着材、リチウム複合酸化物以外の正極活物質等を含有する正極層形成用の塗布液を正極集電体に塗布し、乾燥することで正極層を形成する正極層形成工程、
（１ｂ）負極活物質、溶媒、及び必要に応じて固体電解質、導電材、結着材等を含有する負極層形成用の塗布液を負極集電体に塗布し、乾燥することで負極層を形成する負極層形成工程、
（１ｃ）固体電解質を含有する塗布液を前記正極層及び前記負極層の少なくとも一方に塗布し、乾燥することで固体電解質層又はその一部を形成する固体電解質層形成工程、及び
（１ｄ）前記正極層と前記負極層とを、前記正極層と前記負極層との間に前記固体電解質層又はその一部が挟持されるように貼り合わせ、プレスすることで正極層、固体電解質層及び負極層をこの順に積層する積層工程、
を含む固体電解質含有電池の製造方法。
(1a) For forming a positive electrode layer containing a positive electrode active material according to the first embodiment, a solvent, and if necessary, a solid electrolyte, a conductive material, a binder, a positive electrode active material other than a lithium composite oxide, and the like. A positive electrode layer forming step of applying a coating liquid to a positive electrode current collector and drying it to form a positive electrode layer.
(1b) A coating liquid for forming a negative electrode layer containing a negative electrode active material, a solvent, and if necessary, a solid electrolyte, a conductive material, a binder, and the like is applied to the negative electrode current collector and dried to form a negative electrode layer. Negative electrode layer forming step to be formed,
(1c) A solid electrolyte layer forming step of applying a coating liquid containing a solid electrolyte to at least one of the positive electrode layer and the negative electrode layer and drying to form the solid electrolyte layer or a part thereof, and (1d) the above. The positive electrode layer and the negative electrode layer are bonded to each other so that the solid electrolyte layer or a part thereof is sandwiched between the positive electrode layer and the negative electrode layer, and pressed to obtain a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. Laminating process of laminating in this order,
A method for manufacturing a battery containing a solid electrolyte.
（２ａ）正極活物質、フルオロリン酸化合物、溶媒、及び必要に応じて固体電解質、導電材、結着材等を含有する正極層形成用の塗布液を正極集電体に塗布し、乾燥することで正極層を形成する正極層形成工程、
（２ｂ）負極活物質、溶媒、及び必要に応じて固体電解質、導電材、結着材等を含有する負極層形成用の塗布液を負極集電体に塗布し、乾燥することで負極層を形成する負極層形成工程、
（２ｃ）固体電解質を含有する塗布液を前記正極層及び前記負極層の少なくとも一方に塗布し、乾燥することで固体電解質層又はその一部を形成する固体電解質層形成工程、及び
（２ｄ）前記正極層と前記負極層とを、前記正極層と前記負極層との間に前記固体電解質層又はその一部が挟持されるように貼り合わせ、プレスすることで正極層、固体電解質層及び負極層をこの順に積層する積層工程、
を含む固体電解質含有電池の製造方法。
(2a) A coating liquid for forming a positive electrode layer containing a positive electrode active material, a fluorophosphate compound, a solvent, and if necessary, a solid electrolyte, a conductive material, a binder, and the like is applied to the positive electrode current collector and dried. The positive electrode layer forming step of forming the positive electrode layer,
(2b) A coating liquid for forming a negative electrode layer containing a negative electrode active material, a solvent, and if necessary, a solid electrolyte, a conductive material, a binder, and the like is applied to the negative electrode current collector and dried to form a negative electrode layer. Negative electrode layer forming step to be formed,
(2c) A solid electrolyte layer forming step of applying a coating liquid containing a solid electrolyte to at least one of the positive electrode layer and the negative electrode layer and drying to form the solid electrolyte layer or a part thereof, and (2d) the above. The positive electrode layer and the negative electrode layer are bonded to each other so that the solid electrolyte layer or a part thereof is sandwiched between the positive electrode layer and the negative electrode layer, and pressed to obtain a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. Laminating process of laminating in this order,
A method for manufacturing a battery containing a solid electrolyte.
（３ａ）正極活物質、溶媒、及び必要に応じて固体電解質、導電材、結着材等を含有する正極層形成用の塗布液を正極集電体に塗布し、乾燥することで正極活物質含有層を形成する正極活物質含有層形成工程、
（３ｂ）フルオロリン酸化合物及び溶媒を含有する塗布液を、前記正極活物質含有層に塗布し、乾燥することで正極層を形成する正極層形成工程、
（３ｃ）負極活物質、溶媒、及び必要に応じて固体電解質、導電材、結着材等を含有す
る負極層形成用の塗布液を負極集電体に塗布し、乾燥することで負極層を形成する負極層形成工程、
（３ｄ）固体電解質を含有する塗布液を前記正極層及び前記負極層の少なくとも一方に塗布し、乾燥することで固体電解質層又はその一部を形成する固体電解質層形成工程、及び
（３ｅ）前記正極層と前記負極層とを、前記正極層と前記負極層との間に前記固体電解質層又はその一部が挟持されるように貼り合わせ、プレスすることで正極層、固体電解質層及び負極層をこの順に積層する積層工程、
を含む固体電解質含有電池の製造方法。
(3a) A positive electrode active material is obtained by applying a coating liquid for forming a positive electrode layer containing a positive electrode active material, a solvent, and if necessary, a solid electrolyte, a conductive material, a binder, and the like to a positive electrode current collector and drying the positive electrode active material. Positive electrode active material-containing layer forming step for forming the containing layer,
(3b) A positive electrode layer forming step of applying a coating liquid containing a fluorophosphoric acid compound and a solvent to the positive electrode active material-containing layer and drying to form a positive electrode layer.
(3c) A coating liquid for forming a negative electrode layer containing a negative electrode active material, a solvent, and if necessary, a solid electrolyte, a conductive material, a binder, and the like is applied to the negative electrode current collector and dried to form a negative electrode layer. Negative electrode layer forming step to be formed,
(3d) A solid electrolyte layer forming step of applying a coating liquid containing a solid electrolyte to at least one of the positive electrode layer and the negative electrode layer and drying to form the solid electrolyte layer or a part thereof, and (3e) the above. The positive electrode layer and the negative electrode layer are bonded to each other so that the solid electrolyte layer or a part thereof is sandwiched between the positive electrode layer and the negative electrode layer, and pressed to obtain a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. Laminating process of laminating in this order,
A method for manufacturing a battery containing a solid electrolyte.
（１ａ）～（１ｄ）を含む製造方法は、フルオロリン酸化合物が正極活物質の近傍に分布している態様又は正極活物質を被覆するように分布している態様の実現に好適であり、（２ａ）～（２ｄ）を含む製造方法は、フルオロリン酸化合物が正極活物質、固体電解質等の間に分布している態様の実現に好適である。また、（３ａ）～（３ｅ）を含む製造方法では、正極層と固体電解質層との界面等に分布している態様の実現に好適である。 The production method including (1a) to (1d) is suitable for realizing an embodiment in which the fluorophosphoric acid compound is distributed in the vicinity of the positive electrode active material or a mode in which the fluorophosphoric acid compound is distributed so as to cover the positive electrode active material. The production method containing (2a) to (2d) is suitable for realizing an embodiment in which the fluorophosphoric acid compound is distributed between the positive electrode active material, the solid electrolyte and the like. Further, the production method including (3a) to (3e) is suitable for realizing an embodiment in which the positive electrode layer and the solid electrolyte layer are distributed at the interface or the like.
また、（２ａ）～（２ｄ）を含む製造方法及び（３ａ）～（３ｅ）含む製造方法では、いずれの工程でも、第１の実施形態に係る正極活物質材料を原料として使用していないが、正極活物質がリチウム複合酸化物である場合は、製造過程でリチウム複合酸化物とフルオロリン酸化合物とが互いに接触し、第１の実施形態に係る正極活物質材料が生じる。 Further, in the manufacturing method including (2a) to (2d) and the manufacturing method containing (3a) to (3e), the positive electrode active material material according to the first embodiment is not used as a raw material in any of the steps. When the positive electrode active material is a lithium composite oxide, the lithium composite oxide and the fluorophosphate compound come into contact with each other in the manufacturing process, and the positive electrode active material material according to the first embodiment is produced.
上記製造方法において、各層を形成するために用いる塗布液の溶媒としては、第１の実施形態に係る正極活物質材料の製造に用いる、フルオロリン酸化合物を含有する塗布液の溶媒と同様のものが挙げられる。各層形成工程における塗布液の塗布方法としては、スピンコーティング、ディップコーティング等の公知の塗布方法を採用することができる。また、塗布液の乾燥も、塗布液の溶媒、各層の厚み等に応じて、温度、圧力等の条件を適宜選択して行うことができる。 In the above production method, the solvent of the coating liquid used to form each layer is the same as the solvent of the coating liquid containing the fluorophosphoric acid compound used in the production of the positive electrode active material according to the first embodiment. Can be mentioned. As a coating method of the coating liquid in each layer forming step, a known coating method such as spin coating or dip coating can be adopted. Further, the drying of the coating liquid can also be performed by appropriately selecting conditions such as temperature and pressure according to the solvent of the coating liquid, the thickness of each layer and the like.
なお、負極活物質が金属箔又は金属合金箔である場合、当該金属箔又は金属合金箔は単独で負極として作用し得るため、上記製造方法において、（１ｂ）、（２ｂ）及び（３ｃ）の負極層形成工程を行う必要はなく、当該金属箔又は金属合金箔そのものを負極層かつ負極集電体として用いることができる。 When the negative electrode active material is a metal foil or a metal alloy foil, the metal foil or the metal alloy foil can act alone as a negative electrode. Therefore, in the above manufacturing method, (1b), (2b) and (3c) It is not necessary to perform the negative electrode layer forming step, and the metal foil or the metal alloy foil itself can be used as the negative electrode layer and the negative electrode current collector.
固体電解質含有電池が全固体電池である場合は、例えば上記製造方法（ただし、液状又はゲル状の電解質は使用しないものとする。）の各工程の後に、得られた積層体を電池ケース内部に収納し、電池ケースをかしめることにより、全固体電池を製造することができる。 When the solid electrolyte-containing battery is an all-solid-state battery, for example, after each step of the above manufacturing method (however, a liquid or gel-like electrolyte is not used), the obtained laminate is placed inside the battery case. An all-solid-state battery can be manufactured by storing and crimping the battery case.
以下に、本発明を実施例によって更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例の記載に限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the description of the following examples as long as the gist of the present invention is not exceeded.
＜実施例１＞
（正極活物質材料の製造）
ＬｉＮｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２（０．３ｇ）とジフルオロリン酸リチウムのジメチルカーボネート溶液（濃度１％、０．３ｍＬ）とを混合し、２５℃及び大気圧下で撹拌しながら溶媒を揮発させることにより、ジフルオロリン酸リチウムで被覆された正極活物質材料を得た。レーザ回折・散乱法により測定した正極活物質材料のメジアン径（Ｄ５０）は、７．４μｍであった。
<Example 1>
(Manufacturing of positive electrode active material)
LiNi 0.33 Co 0.33 Mn 0.33 O 2 (0.3 g) and a dimethyl carbonate solution of lithium difluorophosphate (concentration 1%, 0.3 mL) are mixed and stirred at 25 ° C. and atmospheric pressure. While volatilizing the solvent, a positive electrode active material coated with lithium difluorophosphate was obtained. The median diameter (D 50 ) of the positive electrode active material measured by the laser diffraction / scattering method was 7.4 μm.
（全固体電池の製造）
得られた正極活物質材料（４．８ｍｇ）、硫化物系固体電解質（Ｌｉ３ＰＳ４；９．７ｍｇ）及び気相法炭素繊維（０．７ｍｇ）を均一になるまで混合し、混合物を得た。硫化物系固体電解質（Ｌｉ３ＰＳ４；１２０ｍｇ）をＰＥＴ管の中に封じ、プレスすることで形成されたペレット（径１０ｍｍ）の上に、厚さが均一になるように前記混合物（１０．１ｍｇ）を載せてプレスし、正極層／固体電解質層積層体を作製した。得られた正極層／固体電解質層積層体の固体電解質層の上にＩｎ箔とＬｉ箔とをこの順に載せてプレスし、ＰＥＴ管中に正極層／固体電解質層／Ｉｎ－Ｌｉ箔積層体を作製した。得られた正極層／固体電解質層／Ｉｎ－Ｌｉ箔積層体を収納したＰＥＴ管の正極層側及びＩｎ－Ｌｉ箔側にそれぞれ電極ピンを挿入し、さらにＳＵＳ製の外装体に収納して評価用全固体電池を製造した。得られた評価用全固体電池の電池容量及び充放電効率を下記充放電試験により評価した。評価結果を表１に示す。
(Manufacturing of all-solid-state batteries)
The obtained positive electrode active material (4.8 mg), sulfide-based solid electrolyte (Li 3 PS 4 ; 9.7 mg) and vapor phase carbon fiber (0.7 mg) were mixed until uniform to obtain a mixture. rice field. A sulfide-based solid electrolyte (Li 3 PS 4 ; 120 mg) was sealed in a PET tube, and the mixture (10. 1 mg) was placed and pressed to prepare a positive electrode layer / solid electrolyte layer laminate. The In foil and the Li foil are placed in this order on the solid electrolyte layer of the obtained positive electrode layer / solid electrolyte layer laminate and pressed, and the positive electrode layer / solid electrolyte layer / In-Li foil laminate is placed in the PET tube. Made. Electrode pins are inserted into the positive electrode layer side and the In-Li foil side of the PET tube containing the obtained positive electrode layer / solid electrolyte layer / In-Li foil laminate, and further stored in a SUS exterior body for evaluation. Manufactured an all-solid-state battery for use. The battery capacity and charge / discharge efficiency of the obtained all-solid-state battery for evaluation were evaluated by the following charge / discharge test. The evaluation results are shown in Table 1.
＜実施例２～４＞
ジフルオロリン酸リチウムの含有量が表１に示す通りとなるようジフルオロリン酸リチウムのジメチルカーボネート溶液の使用量を変更した以外は、実施例１と同様に評価用全固体電池を製造した、電池容量及び充放電効率を下記充放電試験により評価した。評価結果を表１に示す。
<Examples 2 to 4>
An all-solid-state battery for evaluation was produced in the same manner as in Example 1 except that the amount of the dimethyl carbonate solution of lithium difluorophosphate was changed so that the content of lithium difluorophosphate was as shown in Table 1. And the charge / discharge efficiency was evaluated by the following charge / discharge test. The evaluation results are shown in Table 1.
＜比較例１＞
上記正極活物質材料に変えてＬｉＮｉ０．３３Ｃｏ０．３３Ｍｎ０．３３Ｏ２を使用した以外は、実施例１と同様に評価用全固体電池を製造し、電池容量及び充放電効率を下記充放電試験により評価した。評価結果を表１に示す。
<Comparative Example 1>
An all-solid-state battery for evaluation was manufactured in the same manner as in Example 1 except that LiNi 0.33 Co 0.33 Mn 0.33 O 2 was used instead of the positive electrode active material, and the battery capacity and charge / discharge efficiency were improved. It was evaluated by the following charge / discharge test. The evaluation results are shown in Table 1.
＜充放電試験＞
実施例１～４及び比較例１で製造した評価用全固体電池に対して、以下に示す条件で初回充放電試験を実施し、初回充電容量及び初回充放電効率を算出した。
（初回充放電条件）
試験温度２５℃
充電最大電圧３．６Ｖ，充電電流２５μＡ，定電流定電圧充電，終了電流値１５μＡ
放電最小電圧２．０Ｖ，放電電流２５μＡ，定電流放電
（初回充放電効率の算出）
上記条件で充放電した際の充電容量と、放電容量とから、下記の計算式に基づいて初回充放電効率を求めた。
初回充放電効率（％）
＝初回放電容量（ｍＡｈ／ｇ）／初回充電容量（ｍＡｈ／ｇ）×１００
<Charging / discharging test>
The initial charge / discharge test was carried out on the evaluation all-solid-state batteries manufactured in Examples 1 to 4 and Comparative Example 1 under the following conditions, and the initial charge capacity and the initial charge / discharge efficiency were calculated.
(Initial charge / discharge conditions)
Test temperature 25 ° C
Maximum charging voltage 3.6V, charging current 25μA, constant current constant voltage charging, end current value 15μA
Minimum discharge voltage 2.0V, discharge current 25μA, constant current discharge (calculation of initial charge / discharge efficiency)
The initial charge / discharge efficiency was obtained from the charge capacity and the discharge capacity when charging / discharging under the above conditions based on the following formula.
Initial charge / discharge efficiency (%)
= Initial discharge capacity (mAh / g) / Initial charge capacity (mAh / g) x 100
実施例１～４の正極活物質材料は、リチウム複合酸化物とフルオロリン酸化合物溶液とを混合し、溶媒を揮発させるという簡便な方法により、低消費エネルギーで製造することができた。
また、表１に示された結果から、リチウム複合酸化物１００質量部に対してジフルオロリン酸リチウム０．０４質量部～１．１質量部を含有する正極活物質材料を用いた全固体電池（実施例１～４）は、ジフルオロリン酸リチウムを含有しない正極活物質材料を用いた全固体電池（比較例１）と比較して、３０％以上大きい電池容量を有し、かつ、同等以上の充放電効率を示すことが確認された。
The positive electrode active material of Examples 1 to 4 could be produced with low energy consumption by a simple method of mixing a lithium composite oxide and a fluorophosphoric acid compound solution and volatilizing the solvent.
Further, from the results shown in Table 1, an all-solid-state battery using a positive electrode active material containing 0.04 parts by mass to 1.1 parts by mass of lithium difluorophosphate with respect to 100 parts by mass of the lithium composite oxide (an all-solid-state battery). Examples 1 to 4) have a battery capacity 30% or more larger than that of an all-solid-state battery (Comparative Example 1) using a positive electrode active material that does not contain lithium difluorophosphate, and have the same or higher battery capacity. It was confirmed that it showed charge / discharge efficiency.
本発明に係る正極活物質材料及び固体電解質含有電池は、電池を用いる公知の各種用途に用いることが可能である。具体例としては、例えば、ノートパソコン、ペン入力パソコン、モバイルパソコン、電子ブックプレーヤー、携帯電話、携帯ファックス、携帯コピー、携帯プリンター、ヘッドフォンステレオ、ビデオムービー、液晶テレビ、ハンディークリーナー、ポータブルＣＤ、ミニディスク、トランシーバー、電子手帳、電卓、メモリーカード、携帯テープレコーダー、ラジオ、バックアップ電源、モーター、バイク、原動機付自転車、自転車、照明器具、玩具、ゲーム機器、時計、電動工具、ストロボ、カメラ、家庭用バックアップ電源、事業所用バックアップ電源、負荷平準化用電源、自然エネルギー貯蔵電源等が挙げられる。 The positive electrode active material and the solid electrolyte-containing battery according to the present invention can be used in various known applications using the battery. Specific examples include, for example, laptop computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile fax machines, mobile copies, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, and mini discs. , Transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, bikes, motorized bicycles, bicycles, lighting equipment, toys, game equipment, watches, power tools, strobes, cameras, household backups. Examples include a power source, a backup power source for business establishments, a power source for load leveling, and a renewable energy storage power source.
Claims (8)
モノフルオロリン酸、ジフルオロリン酸及びそれらの塩からなる群より選択される１種以上のフルオロリン酸化合物と、
を含有し、
前記フルオロリン酸化合物の含有量が、前記リチウム複合酸化物１００質量部に対して０．０１質量部以上５．０質量部以下である、固体電解質含有電池用正極活物質材料。 Lithium composite oxide and
One or more fluorophosphate compounds selected from the group consisting of monofluorophosphate, difluorophosphate and salts thereof, and
Contains,
A positive electrode active material for a solid electrolyte-containing battery, wherein the content of the fluorophosphoric acid compound is 0.01 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the lithium composite oxide.
前記正極層又は前記固体電解質層が、モノフルオロリン酸、ジフルオロリン酸及びそれらの塩からなる群より選択される１種以上のフルオロリン酸化合物を含む、固体電解質含有電池。 It has a positive electrode layer, a solid electrolyte layer, and a negative electrode layer in this order.
A solid electrolyte-containing battery in which the positive electrode layer or the solid electrolyte layer contains one or more fluorophosphate compounds selected from the group consisting of monofluorophosphate, difluorophosphate and salts thereof.
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