JP6531887B2 - Positive electrode composite material and all solid lithium-sulfur battery - Google Patents
Positive electrode composite material and all solid lithium-sulfur battery Download PDFInfo
- Publication number
- JP6531887B2 JP6531887B2 JP2014054621A JP2014054621A JP6531887B2 JP 6531887 B2 JP6531887 B2 JP 6531887B2 JP 2014054621 A JP2014054621 A JP 2014054621A JP 2014054621 A JP2014054621 A JP 2014054621A JP 6531887 B2 JP6531887 B2 JP 6531887B2
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- Prior art keywords
- positive electrode
- conductive material
- lithium
- electrode mixture
- sulfur
- Prior art date
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims description 44
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- 239000002131 composite material Substances 0.000 title claims description 30
- 239000004020 conductor Substances 0.000 claims description 113
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 86
- 229910052717 sulfur Inorganic materials 0.000 claims description 53
- 239000007784 solid electrolyte Substances 0.000 claims description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 41
- 239000011593 sulfur Substances 0.000 claims description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims description 39
- 150000002500 ions Chemical class 0.000 claims description 37
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 229920001940 conductive polymer Polymers 0.000 claims description 8
- 238000003701 mechanical milling Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 44
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- -1 for example Inorganic materials 0.000 description 23
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- 239000000126 substance Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
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- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 4
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- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 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
Description
本発明は、正極合材及び全固体型リチウム硫黄電池に関する。 The present invention relates to a positive electrode composite material and an all solid lithium-sulfur battery.
硫黄は、理論容量が約１６７２ｍＡｈ／ｇと非常に高いことが知られており、硫黄を正極活物質として使用したリチウム硫黄電池の研究が盛んに行われている。
リチウム硫黄電池は、電解質として液体電解質を用いた液体型リチウム硫黄電池と、固体電解質を用いた全固体型リチウム硫黄電池とに大別される。
Sulfur is known to have a very high theoretical capacity of about 1672 mAh / g, and research on lithium-sulfur batteries using sulfur as a positive electrode active material has been actively conducted.
Lithium-sulfur batteries are roughly classified into liquid-type lithium-sulfur batteries using a liquid electrolyte as an electrolyte and all-solid-state lithium-sulfur batteries using a solid electrolyte.
液体型リチウム硫黄電池においては、リチウムイオンと硫黄との反応により生成した多硫化リチウムが電解質溶液中に溶け出し、電池の充放電容量や寿命に悪影響を与えることが問題となっていた。 In liquid-type lithium-sulfur batteries, it has been a problem that lithium polysulfide generated by the reaction of lithium ions and sulfur dissolves in the electrolyte solution to adversely affect the charge and discharge capacity and the life of the battery.
これに対し、全固体型リチウム硫黄電池は、多硫化リチウムが電解質溶液に溶け出す問題が生じないため、電池の充放電容量の維持や長寿命化に適している。また、可燃性の有機溶媒を含まないため液漏れや発火のおそれがなく安全性を確保できる点や、セパレータが不要である点等、全固体型リチウム硫黄電池の持つ優れた特性に注目が集まっている。
全固体型リチウム硫黄電池の正極合材層中においては、下記式（１）に示す可逆反応のうち、放電時には右向きの反応が、充電時には左向きの反応が、それぞれ優位に進行している。
Ｓ＋２Ｌｉ＋＋２ｅ− ⇔ Ｌｉ２Ｓ （１）
On the other hand, the all-solid-state lithium-sulfur battery is suitable for maintaining the charge and discharge capacity of the battery and prolonging its life because there is no problem of dissolution of lithium polysulfide into the electrolyte solution. In addition, attention is focused on the superior characteristics of the all-solid-state lithium-sulfur battery, such as that it does not contain a flammable organic solvent and that there is no risk of liquid leakage or ignition and that safety can be ensured, and that a separator is unnecessary. ing.
In the positive electrode mixture layer of the all-solid-state lithium-sulfur battery, among the reversible reactions represented by the following formula (1), a reaction directed rightward at the time of discharge and a reaction directed leftward at the time of charge are respectively advancing.
S + 2Li + + 2e − ⇔ Li 2 S (1)
しかしながら、全固体型リチウム硫黄電池では、負極、固体電解質層及び正極合材層が実質的に溶媒を含有せず、また、正極活物質として正極合材層に含まれる硫黄が電気絶縁性であるため、正極合材層における電子伝導性及びリチウムイオン伝導性が非常に低い。特に、正極合材中に硫黄を高い比率で充填した場合は、充放電に際して上記式（１）に示す反応の反応性が乏しく、十分な充放電容量を確保することができないという課題があった。 However, in the all solid lithium-sulfur battery, the negative electrode, the solid electrolyte layer, and the positive electrode mixture layer do not substantially contain a solvent, and the sulfur contained in the positive electrode mixture layer as a positive electrode active material is electrically insulating Therefore, the electron conductivity and the lithium ion conductivity in the positive electrode mixture layer are very low. In particular, when the positive electrode composite material is filled with sulfur at a high ratio, there is a problem that the reactivity of the reaction represented by the above formula (1) during charge and discharge is poor, and a sufficient charge and discharge capacity can not be secured. .
特許文献１には、全固体リチウム電池の正極に用いる電極材料として、硫黄、導電性物質、並びに、リチウム原子、リン原子及び硫黄原子を含む固体電解質を含む電極材料が提案されている。この文献では、上述した電極材料によれば、全固体リチウム電池の電池性能を高めることができるとされている。 Patent Document 1 proposes an electrode material containing sulfur, a conductive substance, and a solid electrolyte containing a lithium atom, a phosphorus atom and a sulfur atom as an electrode material used for a positive electrode of an all solid lithium battery. In this document, according to the electrode material mentioned above, it is supposed that the battery performance of the all solid lithium battery can be improved.
しかしながら、実際のところ、特許文献１に記載された全固体リチウム電池用電極材料では、スマートフォンやパソコン等の低出力用途を想定したとしても非実用的な低電流で使用する場合はまだしも、実用的な電流で使用する場合には充分な充放電容量を確保することが困難であった。
即ち、従来の正極合材層を備えた全固体型リチウム硫黄電池では、充放電容量について未だ改善の必要があり、実用的な高電流での使用にも耐え得る全固体型リチウム硫黄電池を実現する上で、硫黄の持つ優れた物性を活かしきれていないとの課題があった。
However, in fact, in the electrode material for an all solid lithium battery described in Patent Document 1, even if low power applications such as smartphones and personal computers are assumed, it is still practical when used at impractical low current. It is difficult to secure sufficient charge and discharge capacity when using at a low current.
That is, in the all-solid-state lithium-sulfur battery provided with the conventional positive electrode composite material layer, it is still necessary to improve the charge and discharge capacity, and an all-solid-state lithium-sulfur battery that can withstand practical high current use is realized In doing so, there was a problem that the excellent physical properties of sulfur could not be utilized.
本発明は、硫黄の持つ優れた物性を最大限に活かし、優れた正極合材当たりの充放電容量を有する全固体型リチウム硫黄電池の正極合材層に好適に用いることができる正極合材を提供することを目的とする。また、上記正極合材を含む正極合材層を備えた全固体型リチウム硫黄電池を提供することを目的とする。 The present invention is a positive electrode composite material that can be suitably used for the positive electrode composite material layer of the all solid lithium-sulfur battery having excellent charge and discharge capacity per positive electrode composite material by making the best use of the excellent physical properties of sulfur. Intended to be provided. Another object of the present invention is to provide an all solid lithium-sulfur battery provided with a positive electrode mixture layer containing the above-mentioned positive electrode mixture.
本発明者らは、全固体型リチウム硫黄電池に用いる正極合材について種々検討したところ、イオン伝導性物質と硫黄及び／又はその放電生成物と導電材とを含む正極合材において、導電材として、１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭を用いることにより、電気絶縁体の正極活物質を正極合材中に高い比率で充填した状態においても、正極合材内の電子抵抗を効果的に低減できるため、上記式（１）で示す反応の反応性が向上する結果、全固体型リチウム硫黄電池の正極合材当たりの充放電容量、特に高電流を流した際の充放電容量が向上するとの新たな知見を得、この知見に基づき本発明を完成した。 The present inventors have variously examined positive electrode mixtures used for all solid-state lithium-sulfur batteries. As a conductive material, a positive electrode mixture containing an ion conductive material, sulfur and / or its discharge product and a conductive material By using activated carbon coated with a conductive material having a conductivity of 1 S / cm or more, even in the state where the positive electrode active material of the electrical insulator is filled in the positive electrode mixture at a high ratio, the electrons in the positive electrode mixture Since the resistance can be effectively reduced, the reactivity of the reaction represented by the above formula (1) is improved. As a result, the charge / discharge capacity per positive electrode mixture of the all-solid-state lithium-sulfur battery, in particular when charging a high current New findings were obtained that the discharge capacity was improved, and the present invention was completed based on the findings.
即ち、本発明の正極合材は以下に関する：
［１］
［Ａ］硫黄及び／又はその放電生成物、
［Ｂ］イオン伝導性物質、並びに、
［Ｃ］１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭
の成分を含み、全固体型リチウム硫黄電池の正極合材層に用いられることを特徴とする正極合材；
［２］
活性炭のＢＥＴ比表面積が１０００ｍ２／ｇ以上である、［１］の正極合材；
［３］
導電材料が導電性高分子である、［１］又は［２］の正極合材；
［４］
成分［Ｂ］がＰｘＳｙ（ここで、ｘ及びｙは、独立して、化学量論比を与える整数を表わす）又はＬｉとＳとＰとを含む複合化物であり、Ｐの重量比が０．１５〜０．５５である、［１］〜［３］のいずれかの正極合材；
［５］
ＬｉとＳとＰとを含む複合化物が、少なくともＬｉ２ＳとＳとＰとを、又は、少なくともＬｉ２ＳとＰｘＳｙ（ここで、ｘ及びｙは、独立して、化学量論比を与える整数を表わす）とをメカニカルミリング処理することにより得られたものである、［４］の正極合材；
［６］
ＬｉとＳとＰとを含む複合化物が、ＭｚＳ（ここで、Ｍは、Ｓｉ、Ｇｅ、Ｂ又はＡｌを表わし、Ｚは、化学量論比を与える整数をそれぞれ表わす）、酸化リン、酸化リチウム及びヨウ化リチウムからなる群より選択される少なくとも１つを、Ｌｉ２Ｓ、Ｓ及びＰ、又は、Ｌｉ２Ｓ及びＰｘＳｙとともにメカニカルミリング処理することにより得られたものである、［５］の正極合材；
［７］
成分［Ａ］の含有量が正極合材全体の４０重量％以上である、［１］〜［６］のいずれかの正極合材；
［８］
［１］〜［７］のいずれかの正極合材を含む正極合材層、固体電解質層、負極及び集電体を備えることを特徴とする全固体型リチウム硫黄電池。
That is, the positive electrode composite material of the present invention relates to the following:
[1]
[A] Sulfur and / or its discharge product,
[B] ion conductive material, and
[C] A positive electrode mixture containing a component of activated carbon coated with a conductive material having a conductivity of 1 S / cm or more and used in a positive electrode mixture layer of an all solid lithium-sulfur battery;
[2]
The positive electrode composite material of [1], wherein the BET specific surface area of the activated carbon is 1000 m 2 / g or more;
[3]
The positive electrode mixture material of [1] or [2], wherein the conductive material is a conductive polymer;
[4]
Component [B] is P x S y (where x and y independently represent an integer giving a stoichiometric ratio) or a complex comprising Li and S and P, and the weight ratio of P is The positive electrode mixture according to any one of [1] to [3], wherein
[5]
A complex comprising Li, S and P at least Li 2 S, S and P, or at least Li 2 S and P x S y (where x and y are independently stoichiometries A positive electrode mixture material of [4] which is obtained by subjecting an integer which gives a ratio to a mechanical milling process;
[6]
A complex comprising Li, S and P is M z S (where M represents Si, Ge, B or Al, and Z represents an integer giving a stoichiometric ratio, respectively), phosphorus oxide, It is obtained by mechanical milling at least one selected from the group consisting of lithium oxide and lithium iodide with Li 2 S, S and P, or Li 2 S and P x S y , Composite material of [5];
[7]
The positive electrode mixture according to any one of [1] to [6], wherein the content of the component [A] is 40% by weight or more of the entire positive electrode mixture;
[8]
An all-solid-state lithium-sulfur battery comprising a positive electrode mixture layer containing a positive electrode mixture according to any one of [1] to [7], a solid electrolyte layer, a negative electrode, and a current collector.
本発明の正極合材は、導電材として、１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭を用いるため、全固体型リチウム硫黄電池の正極合材層として用いた場合に、正極合材にて正極活物質である硫黄及び／又はその放電生成物の含有率を高くした場合においても、電子抵抗を低い状態に維持できるため、充放電特性に優れた全固体型リチウム硫黄電池を提供することができる。特に、低電流（例えば、０．１〜０．５ｍＡ／ｃｍ２程度）で使用した場合は勿論のこと、高電流（例えば、１ｍＡ／ｃｍ２以上）で使用した場合でも高い充放電容量を有する点で本発明は優れる。
また、本発明の全固体型リチウム硫黄電池は、本発明の正極合材を含む正極合材層を備えるため、充放電特性に優れる。
そして、このような正極合材及びこの正極合材を用いた全固体型リチウム硫黄電池は、例えば、電気自動車やハイブリッド自動車に使用することができるため、本発明によればＣＯ２削減に貢献することができる。
Since the positive electrode mixture of the present invention uses activated carbon coated with a conductive material having a conductivity of 1 S / cm or more as the conductive material, the positive electrode is used when it is used as a positive electrode mixture layer of an all solid lithium-sulfur battery Even when the content of sulfur and / or its discharge product, which is a positive electrode active material, is increased in the composite material, the electronic resistance can be maintained in a low state, so an all solid lithium sulfur battery excellent in charge and discharge characteristics. Can be provided. In particular, low current (e.g., 0.1~0.5mA / cm 2 or so) of course when used in, has a high charge and discharge capacity even when used at a high current (e.g., 1 mA / cm 2 or higher) The present invention is excellent in point.
In addition, the all-solid-state lithium-sulfur battery of the present invention is excellent in charge and discharge characteristics since it includes the positive electrode mixture layer containing the positive electrode mixture of the present invention.
And since such a positive electrode composite material and the all-solid-state lithium-sulfur battery using this positive electrode composite material can be used, for example, in electric vehicles and hybrid vehicles, the present invention contributes to CO 2 reduction. be able to.
＜＜正極合材＞＞
まず、本発明の正極合材について説明する。
本発明の正極合材は、全固体型リチウム硫黄電池の正極合材層に用いる正極合材であり、
［Ａ］硫黄及び／又はその放電生成物、
［Ｂ］イオン伝導性物質、並びに、
［Ｃ］１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭
の成分を含むことを特徴とする。
<< Positive electrode composite material >>
First, the positive electrode composite material of the present invention will be described.
The positive electrode mixture material of the present invention is a positive electrode mixture material used for the positive electrode mixture layer of the all solid lithium-sulfur battery,
[A] Sulfur and / or its discharge product,
[B] ion conductive material, and
[C] characterized by including a component of activated carbon coated with a conductive material having a conductivity of 1 S / cm or more.
＜硫黄及び／又はその放電生成物［Ａ］＞
本発明の正極合材は、正極活物質として上記硫黄及び／又はその放電生成物［Ａ］を含有する（以下、成分［Ａ］ともいう）。
上記硫黄としては、単体の硫黄等を用いることができる。
上記硫黄の放電生成物としては特に限定されないが、例えば、Ｌｉ２Ｓ８、Ｌｉ２Ｓ４、Ｌｉ２Ｓ２等の多硫化リチウムや、硫化リチウム（Ｌｉ２Ｓ）等を用いることができる。これらの化合物は、単独で用いても良いし、２種以上を併用しても良く、更には単体の硫黄と併用しても良い。
<Sulfur and / or its discharge product [A]>
The positive electrode mixture material of the present invention contains the above sulfur and / or its discharge product [A] as a positive electrode active material (hereinafter, also referred to as component [A]).
As said sulfur, elemental sulfur etc. can be used.
The discharge product of sulfur is not particularly limited, and, for example, lithium polysulfide such as Li 2 S 8 , Li 2 S 4 , Li 2 S 2 or the like, lithium sulfide (Li 2 S) or the like can be used. These compounds may be used alone or in combination of two or more, and may be used in combination with elemental sulfur.
上記硫黄及び／又はその放電生成物［Ａ］は、正極合材中での反応性を向上させる目的で、後述するイオン伝導性物質［Ｂ］や導電材［Ｃ］といった他の成分と混合する前に、予めＰｘＳｙ（ここで、ｘ及びｙは、独立して、化学量論比を与える整数を表わす）や単体リンと混合したものを用いても良い（イオン伝導性物質［Ｂ］がＰｘＳｙの場合について、イオン伝導性物質［Ｂ］としてのＰｘＳｙの全て又は一部を上記硫黄及び／又はその放電生成物［Ａ］と予め混合しても良い）。この場合、ＰｘＳｙ又は単体リンは、上記硫黄及び／又はその放電生成物［Ａ］に対して１〜３５重量％の使用量であることが好ましい。 The sulfur and / or the discharge product [A] is mixed with other components such as the ion conductive material [B] and the conductive material [C] described later for the purpose of improving the reactivity in the positive electrode mixture. Alternatively, it may be used in advance mixed with P x S y (where, x and y independently represent an integer giving a stoichiometric ratio) or a single phosphorus (ion conductive substance [B ] for the case of P x S y, it may be all or a portion of P x S y as ion conductive material [B] premixed with the sulfur and / or discharge products thereof [a]). In this case, P x S y or elemental phosphorus is preferably used in an amount of 1 to 35% by weight based on the sulfur and / or the discharge product [A].
＜イオン伝導性物質［Ｂ］＞
上記イオン伝導性物質［Ｂ］は、本発明の正極合材に固体電解質として含まれるものである（以下、成分［Ｂ］ともいう）。
上記イオン伝導性物質［Ｂ］としては特に限定されず、本件技術分野で使用されるイオン伝導性物質を使用することができる。
上記イオン伝導性物質［Ｂ］としてはリンを含有するものが好ましく、その具体例としては、例えば、ＰｘＳｙ（ここで、ｘ及びｙは、独立して、化学量論比を与える整数を表わす）、ＬｉとＳとＰとを含む複合化物等が挙げられる。
これらは、単独で用いても良いし、２種以上を併用しても良い。
<Ion conductive substance [B]>
The ion conductive substance [B] is contained as a solid electrolyte in the positive electrode composite material of the present invention (hereinafter, also referred to as component [B]).
The ion conductive material [B] is not particularly limited, and the ion conductive material used in the present technical field can be used.
The ion conductive substance [B] preferably contains phosphorus, and as a specific example thereof, for example, P x S y (where, x and y independently represent an integer giving a stoichiometric ratio) And complex compounds containing Li, S and P, and the like.
These may be used alone or in combination of two or more.
また、上記イオン伝導性物質［Ｂ］がリンを含有する場合、リンの重量比が０．１５〜０．５５であることが好ましい。このような特定量のリンを含有するイオン伝導性物質を用いることにより、正極合材層中で、硫黄、電子及びリチウムイオンが反応界面で反応する際の抵抗を小さくすることができ、全固体型リチウム硫黄電池の充放電容量をさらに向上させることができる。
一方、上記（Ｃ）イオン伝導性物質において、リンの重量比が０．１５未満の場合や、０．５５を超える場合には、全固体型リチウム硫黄電池に用いた場合に充電時に流す又は放電時に流れる電流値の大きさによっては、充分な充放電容量を確保することができないことがあり、好ましくない。
Moreover, when the said ion conductive material [B] contains phosphorus, it is preferable that the weight ratio of phosphorus is 0.15-0.55. By using an ion conductive substance containing such a specific amount of phosphorus, the resistance when sulfur, electrons and lithium ions react at the reaction interface can be reduced in the positive electrode mixture layer, and all solids are obtained. The charge-discharge capacity of the lithium-sulfur battery can be further improved.
On the other hand, in the above (C) ion conductive material, when the weight ratio of phosphorus is less than 0.15 or exceeds 0.55, when used in an all-solid-state lithium-sulfur battery, flow or discharge during charging Depending on the magnitude of the current value flowing sometimes, sufficient charge / discharge capacity may not be secured, which is not preferable.
上記ＬｉとＳとＰとを含む複合化物としては、少なくともＬｉ２ＳとＳとＰとをメカニカルミリング処理することにより得た複合化物（以下、単にＬｉ２ＳとＳとＰとの複合化物という）や、少なくともＬｉ２ＳとＰｘＳｙ（ここで、ｘ及びｙは、独立して、化学量論比を与える整数を表わす）とをメカニカルミリング処理することにより得た複合化物（以下、単にＬｉ２ＳとＰｘＳｙとの複合化物という）が好ましい。
その理由は、メカニカルミリング処理することで簡易に結合を再配列することができ、かつ、アモルファス状のイオン伝導性物質が得られるからである。
As the composite containing Li, S and P, a composite obtained by mechanical milling at least Li 2 S, S and P (hereinafter simply referred to as a composite of Li 2 S, S and P), A complex obtained by mechanical milling at least Li 2 S and P x S y (where x and y independently represent an integer giving a stoichiometric ratio) (hereinafter simply Li 2 ) and a complex of P x S y ) is preferable.
The reason is that bonding can be easily rearranged by mechanical milling, and an amorphous ion conductive material can be obtained.
本発明において、「複合化物」とは、単に所定の成分が混合されたものではなく、所定の成分が混合されたものに機械的、熱的又は化学的なエネルギーが加えられ、所定の成分の全部又は一部に化学反応が生じたものをいう。
また、本明細書において、「複合化する」とは、単に所定の成分を混合することではなく、所定の成分を混合したものに機械的、熱的又は化学的なエネルギーを加えることにより、所定の成分の全部又は一部に化学反応を生じさせることをいう。
In the present invention, “complex” is not merely a mixture of predetermined components, but mechanical, thermal or chemical energy is added to a mixture of predetermined components to obtain a predetermined component. A chemical reaction has occurred in whole or in part.
In addition, in the present specification, “combining” is not simply mixing the predetermined components, but adding mechanical, thermal or chemical energy to a mixture of the predetermined components. The chemical reaction is caused in all or part of the components of
上記イオン伝導性物質［Ｂ］が、上記Ｌｉ２ＳとＳとＰとの複合化物及び上記Ｌｉ２ＳとＰｘＳｙとの複合化物のいずれかである場合、それぞれの複合化物において、Ｌｉ２Ｓの占めるモル比は任意であるが、複合化物中に含まれるリンの含有量が重量比で０．１５〜０．５５となる量であることが好ましい。 In the case where the ion conductive substance [B] is either a complex of Li 2 S, S and P or a complex of Li 2 S and P x S y , Li in each complex is The molar ratio of 2 S is arbitrary, but it is preferable that the content of phosphorus contained in the composite is in the range of 0.15 to 0.55 by weight.
上記メカニカルミリング処理としては、従来公知の方法を用いることができ、その具体例としては、例えば、遊星ボールミルを用いて、自転速度２２５〜５００ｒｐｍ、公転速度４５０〜１０００ｒｐｍ（自転と逆回転）で０．５〜１０時間処理する方法等が挙げられる。
なお、Ｌｉ２ＳとＰｘＳｙとが複合化したものか、又は、Ｌｉ２ＳとＰｘＳｙとが単に混合しただけのものかは、ラマン分光法により確認することができる。例えば、Ｌｉ２ＳとＰ２Ｓ５との複合化物の場合、複合化に使用した原料であるＰ２Ｓ５由来の３００ｃｍ−１のピークが消失するか、又は、４００ｃｍ−１付近の主ピークに対して相対的に小さくなることから、Ｌｉ２ＳとＰ２Ｓ５とが複合化したことを確認することができる。
As the mechanical milling treatment, a conventionally known method can be used, and as a specific example thereof, for example, using a planetary ball mill, 0 at a rotation speed of 225 to 500 rpm and a revolution speed of 450 to 1000 rpm (rotation and reverse rotation) The method etc. of processing for 5 to 10 hours are mentioned.
It can be confirmed by Raman spectroscopy whether Li 2 S and P x S y are complexed or Li 2 S and P x S y are merely mixed. For example, in the case of a complex of Li 2 S and P 2 S 5 , the peak of 300 cm −1 derived from P 2 S 5 which is the raw material used for complexing disappears, or the main peak around 400 cm −1 Since it becomes relatively small with respect to, it can be confirmed that Li 2 S and P 2 S 5 are complexed.
上記ＬｉとＳとＰとを含む複合化物は、イオン伝導性をさらに向上させることができる場合があることから、ＭｚＳ（ここで、Ｍは、Ｓｉ、Ｇｅ、Ｂ又はＡｌを、Ｚは、化学量論比を与える整数をそれぞれ表わす）、酸化リン、酸化リチウム及びヨウ化リチウムからなる群より選択される少なくとも１つを、Ｌｉ２Ｓ、Ｓ及びＰ、又は、Ｌｉ２Ｓ及びＰｘＳｙとともにメカニカルミリング処理することにより得られたものであっても良い。 Since a complex comprising the above Li, S and P may be able to further improve the ion conductivity, M z S (wherein M is Si, Ge, B or Al, and Z is , At least one selected from the group consisting of phosphorous oxide, lithium oxide and lithium iodide, Li 2 S, S and P, or Li 2 S and P x with S y may be those obtained by mechanical milling.
また、同様の理由で、上記ＬｉとＳとＰとを含む複合化物は、リチウム塩やリチウム窒化物を更に含んでいても良い。
上記リチウム塩としては特に限定されないが、例えば、Ｌｉ３ＰＯ４、Ｌｉ４ＳｉＯ４、ＬｉＢＨ４等が挙げられる。
また、上記リチウム窒化物としては特に限定されないが、例えば、Ｌｉ３Ｎ等が挙げられる。
Further, for the same reason, the complex compound containing Li, S and P may further contain a lithium salt or lithium nitride.
Is not particularly restricted but includes lithium salt, for example, Li 3 PO 4, Li 4 SiO 4, LiBH 4 , and the like.
Further, the lithium nitride is not particularly limited, and examples thereof include Li 3 N and the like.
＜導電材［Ｃ］＞
本発明の正極合材は、電子伝導体として１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭を含有する（以下、導電材［Ｃ］ともいう）。
<Conductive material [C]>
The positive electrode mixture material of the present invention contains activated carbon coated with a conductive material having a conductivity of 1 S / cm or more as an electron conductor (hereinafter, also referred to as a conductive material [C]).
上記導電材［Ｃ］に用いる活性炭のＢＥＴ比表面積は、１０００ｍ２／ｇ以上であることが好ましく、１５００ｍ２／ｇ以上であることがより好ましい。
上記ＢＥＴ比表面積が１０００ｍ２／ｇ未満であると、硫黄及び／又はその放電生成物［Ａ］との反応界面の面積が小さくなる結果、反応抵抗が増大し、充放電容量が小さくなることがある。
一方、本発明における活性炭のＢＥＴ比表面積の好ましい上限は、５０００ｍ２／ｇである。
The BET specific surface area of the activated carbon used for the conductive material [C] is preferably 1000 m 2 / g or more, and more preferably 1500 m 2 / g or more.
When the BET specific surface area is less than 1000 m 2 / g, the area of the reaction interface with sulfur and / or its discharge product [A] becomes small, and as a result, the reaction resistance increases and the charge / discharge capacity becomes small. is there.
On the other hand, the preferable upper limit of the BET specific surface area of the activated carbon in the present invention is 5000 m 2 / g.
本明細書において、ＢＥＴ比表面積とは、Ｂｒｅｎａｕｅｒ−Ｅｍｍｅｔ−Ｔｅｌｌｅ（ＢＥＴ）法により求めた比表面積をいい、具体的には、導電性カーボンのサンプルを液体窒素温度下において、サンプルに窒素ガスを吸着して得られる窒素吸着等温線を用いて求めた比表面積をいう。
上記ＢＥＴ比表面積を求めるための測定装置としては、例えば、自動比表面積／細孔分布測定装置（日本ベル株式会社製、ＢＥＬＳＯＲＰ−ｍｉｎｉ ＩＩ）を用いることができる。
In the present specification, BET specific surface area refers to the specific surface area determined by the Brenauer-Emmet-Telle (BET) method. Specifically, a sample of conductive carbon is subjected to nitrogen gas at the temperature of liquid nitrogen, and the sample is The specific surface area determined using the nitrogen adsorption isotherm obtained by adsorption.
As a measuring apparatus for calculating | requiring the said BET specific surface area, an automatic specific surface area / pore distribution measuring apparatus (Nippon-Bell Co., Ltd. make, BELSORP-mini II) can be used, for example.
上記活性炭を被覆するための１Ｓ／ｃｍ以上の導電率を有する導電材料としては特に限定されないが、例えば、ファーネスブラック（中空シェル構造を有するファーネスブラックを含む）、カーボンナノチューブ、グラフェン、金属微粒子、金属ナノワイヤ、金属メッシュ、導電性高分子等が挙げられる。 The conductive material having a conductivity of 1 S / cm or more for coating the activated carbon is not particularly limited. For example, furnace black (including furnace black having a hollow shell structure), carbon nanotubes, graphene, metal fine particles, metal A nanowire, a metal mesh, a conductive polymer etc. are mentioned.
上記中空シェル構造を有するファーネスブラックとは、導電性ファーネスブラックの一種であり、空隙率は６０〜８０％程度の中空シェル状の構造を持つものをいう。ここで「中空シェル構造」とは、黒鉛結晶が薄く寄り集まって粒子形態の外殻を形成し、外殻の内側に空隙を有する構造をいう。上記中空シェル構造を有するファーネスブラックとしては、例えば、ケッチェンブラック（ライオン社製）等が挙げられる。 The above-mentioned furnace black having a hollow shell structure is a kind of conductive furnace black and has a hollow shell structure having a porosity of about 60 to 80%. Here, the “hollow shell structure” refers to a structure in which graphite crystals are gathered thinly to form an outer shell in the form of particles, and a void is formed inside the outer shell. Examples of the furnace black having a hollow shell structure include ketjen black (manufactured by Lion Corporation).
導電性高分子としては特に限定されず、従来公知の導電性高分子を用いることができ、具体例としては、例えば、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレン、ポリフェニレンビニレン、ポリナフタレン、これらの誘導体、及び、これらとポリ陰イオン（ドーパント）との複合体等が挙げられる。
これらの導電性高分子は単独で用いても良いし、２種以上を併用しても良い。
The conductive polymer is not particularly limited, and conventionally known conductive polymers can be used. Specific examples thereof include, for example, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, derivatives thereof, and derivatives thereof And complexes of these with poly anions (dopant).
These conductive polymers may be used alone or in combination of two or more.
導電性高分子としては、ポリ（３，４−二置換チオフェン）、又は、ポリ（３，４−二置換チオフェン）がより好ましい。導電性や化学的安定性に極めて優れているからである。 As the conductive polymer, poly (3,4-disubstituted thiophene) or poly (3,4-disubstituted thiophene) is more preferable. It is because it is extremely excellent in conductivity and chemical stability.
ポリ（３，４−二置換チオフェン）としては、ポリ（３，４−ジアルコキシチオフェン）又はポリ（３，４−アルキレンジオキシチオフェン）が特に好ましく、ポリ（３，４−ジアルコキシチオフェン）又はポリ（３，４−アルキレンジオキシチオフェン）としては、以下の式（Ｉ）：
で示される反復構造単位からなる陽イオン形態のポリチオフェンが挙げられる。
As poly (3,4-disubstituted thiophene), poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferable, and poly (3,4-dialkoxythiophene) or As poly (3,4-alkylenedioxythiophene), the following formula (I):
And polythiophene in a cationic form consisting of repeating structural units represented by
Ｃ１−４のアルキル基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基等が挙げられる。
また、Ｒ１及びＲ２が結合している場合、Ｃ１−４のアルキレン基としては、特に限定されないが、例えば、メチレン基、１，２−エチレン基、１，３−プロピレン基、１，４−ブチレン基、１−メチル−１，２−エチレン基、１−エチル−１，２−エチレン基、１−メチル−１，３−プロピレン基、２−メチル−１，３−プロピレン基等が挙げられる。これらの中では、メチレン基、１，２−エチレン基、１，３−プロピレン基が好ましく、１，２−エチレン基がより好ましい。
Ｃ１−４のアルキル基、及び、Ｃ１−４のアルキレン基は、その水素の一部が置換されていても良い。Ｃ１−４のアルキレン基を有するポリチオフェンとしては、ポリ（３，４−エチレンジオキシチオフェン）が特に好ましい。
The C 1-4 alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. .
In addition, when R 1 and R 2 are bonded, the C 1-4 alkylene group is not particularly limited, and examples thereof include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, and 1,1, 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. It can be mentioned. Among these, a methylene group, a 1,2-ethylene group and a 1,3-propylene group are preferable, and a 1,2-ethylene group is more preferable.
The C 1-4 alkyl group and the C 1-4 alkylene group may have part of their hydrogens substituted. As the polythiophene having a C 1-4 alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.
上述のポリ（３，４−二置換チオフェン）やポリ（３，４−二置換チオフェン）としては、導電性や溶媒中での分散安定性を向上させる目的で、ポリ陰イオンとの複合体を形成させたものを用いても良い。
ポリ陰イオンとしては、特に限定されないが、例えば、カルボン酸ポリマー類（例えば、ポリアクリル酸、ポリマレイン酸、ポリメタクリル酸等）、スルホン酸ポリマー類（例えば、ポリスチレンスルホン酸、ポリビニルスルホン酸、ポリイソプレンスルホン酸等）等が挙げられる。これらのカルボン酸ポリマー類及びスルホン酸ポリマー類はまた、ビニルカルボン酸類及びビニルスルホン酸類と他の重合可能なモノマー類、例えば、アクリレート類、スチレン、ビニルナフタレン等の芳香族ビニル化合物との共重合体であっても良い。これらの中では、ポリスチレンスルホン酸が特に好ましい。
As the above-mentioned poly (3,4-disubstituted thiophene) and poly (3,4-disubstituted thiophene), in order to improve the conductivity and dispersion stability in a solvent, a complex with a polyanion is You may use what was formed.
Examples of poly anions include, but are not limited to, carboxylic acid polymers (eg, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (eg, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene) Sulfonic acid etc. etc. may be mentioned. These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers, such as acrylates, aromatic vinyl compounds such as styrene, vinyl naphthalene and the like. It may be Among these, polystyrene sulfonic acid is particularly preferred.
上記導電材［Ｃ］は、例えば、１Ｓ／ｃｍ以上の導電率を有する導電材料を含む溶液又は分散液に活性炭を浸漬し、活性炭を上記導電材料で被覆する工程（ａ）、及び、工程（ａ）で得られた１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭を溶液又は分散液から分離する工程（ｂ）を経て得ることができる。 The conductive material [C] is, for example, a step (a) of immersing activated carbon in a solution or dispersion containing a conductive material having a conductivity of 1 S / cm or more, and coating the activated carbon with the conductive material; The activated carbon coated with the conductive material having a conductivity of 1 S / cm or more obtained in a) can be obtained through the step (b) of separating from the solution or the dispersion.
１Ｓ／ｃｍ以上の導電率を有する導電材料を溶解又は分散させる溶媒又は分散媒としては、上記導電材料を溶解又は分散させるために通常使用されるものを使用すれば良い。 As a solvent or dispersion medium for dissolving or dispersing a conductive material having a conductivity of 1 S / cm or more, those generally used for dissolving or dispersing the above-mentioned conductive material may be used.
工程（ａ）では、必要に応じて、超音波処理、撹拌処理等の処理を行っても良い。
超音波処理は、活性炭の二次粒子の分散を目的に行うものであり、その条件は特に限定されないが、例えば、発振周波数２０〜５０Ｈｚの条件下、１〜５００分間行うことができる。
撹拌処理は、特に限定されないが、例えば、マグネチックスターラー、メカニカルスターラー、振とう機等を用いて、使用する溶媒の融点より高く、沸点以下の温度範囲で１０分間〜５００時間の条件で行うことができる。
これらの処理を行うことより、活性炭をより均一に上記導電材料で被覆することができる。
In the step (a), treatments such as ultrasonic treatment and stirring may be performed as necessary.
The ultrasonic treatment is performed for the purpose of dispersing secondary particles of activated carbon, and the conditions are not particularly limited. For example, the ultrasonic treatment can be performed for 1 to 500 minutes under an oscillation frequency of 20 to 50 Hz.
The stirring treatment is not particularly limited, but for example, using a magnetic stirrer, a mechanical stirrer, a shaker or the like, it is carried out at a temperature range higher than the melting point of the solvent used and at a temperature not higher than the boiling point for 10 minutes to 500 hours. Can.
By performing these treatments, activated carbon can be coated with the conductive material more uniformly.
工程（ｂ）における、工程（ａ）で得られた１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭を硫黄溶液から分離する方法としては、特に限定されないが、溶媒留去、濾過、遠心分離、デカンテーション等の公知の方法を用いることができる。濾過としては、特に限定されないが、例えば、自然濾過、吸引濾過（減圧濾過）、加圧濾過、遠心濾過等を採用することができる。 The method for separating the activated carbon coated with the conductive material having a conductivity of 1 S / cm or more obtained in step (a) in step (b) from the sulfur solution is not particularly limited. Known methods such as centrifugation, decantation and the like can be used. Although it does not specifically limit as filtration, For example, natural filtration, suction filtration (vacuum filtration), pressure filtration, centrifugal filtration etc. are employable.
工程（ａ）及び工程（ｂ）に加えて、工程（ｂ）において分離された活性炭を加熱処理する工程（ｃ）を行っても良い。工程（ｃ）を行うことにより、上記導電材料で被覆された活性炭に残存する溶媒をより確実に除去することができる。
なお、工程（ｃ）においては、複数回の加熱処理を、温度条件を変えながら段階的に行っても良い。
In addition to the steps (a) and (b), the activated carbon separated in the step (b) may be heat-treated (c). By performing the step (c), the solvent remaining on the activated carbon coated with the conductive material can be more reliably removed.
In the step (c), the heat treatment may be performed plural times while changing the temperature conditions.
工程（ｃ）における、上記導電材料で被覆された活性炭の加熱処理は、特に限定されないが、例えば、アルゴン、窒素、空気等の雰囲気下、１秒間〜１００時間行うことができる。また、導電性高分子といった導電材料が分解しない条件で、減圧して行っても良い。加熱処理（工程（ｃ）において、複数回の加熱処理を温度条件を変えながら段階的に行う場合には、最後の加熱処理）の温度は、特に限定されないが、６０℃以上とすることが好ましく、１００℃以上とすることがより好ましい。温度が６０℃未満であると、溶媒が残存する場合がある。加熱処理の温度の上限は特に限定されないが、２５０℃とすることが好ましい。
なお、加熱処理は、従来公知の乾燥装置を用いて行えばよく、具体的には、例えば、定温乾燥機、送風乾燥機、減圧乾燥機、赤外線乾燥機等を用いて行えばよい。
The heat treatment of the activated carbon coated with the conductive material in the step (c) is not particularly limited, but can be performed, for example, under an atmosphere of argon, nitrogen, air, etc., for 1 second to 100 hours. Alternatively, pressure reduction may be performed under the condition that the conductive material such as the conductive polymer is not decomposed. The temperature of the heat treatment (in the step (c), when the heat treatment is performed a plurality of times stepwise while changing the temperature conditions, the temperature of the last heat treatment) is not particularly limited, but preferably 60 ° C. or higher And 100 ° C. or more are more preferable. If the temperature is less than 60 ° C., the solvent may remain. The upper limit of the temperature of the heat treatment is not particularly limited, but is preferably 250 ° C.
The heat treatment may be performed using a conventionally known drying device, and specifically, may be performed using, for example, a constant temperature dryer, a blower dryer, a reduced pressure dryer, an infrared dryer, or the like.
本製造方法において、導電材料の種類と量、溶媒・分散媒の種類と量、活性炭の導電材料溶液・分散液への浸漬時間、撹拌条件、各工程における温度等を調整することにより活性炭を被覆する導電材料の膜厚を制御することができる。例えば、導電材料の膜厚を厚くするためには、初めは温度を高くして導電材料溶液の濃度を高めておき、活性炭の被覆に伴い導電材料溶液の濃度が低下するに従い、導電材料の飽和濃度を超えないように注意しながら、徐々に温度を下げて行くと良い。
本発明の正極合材において、導電材［Ｃ］は、活性炭が１Ｓ／ｃｍ以上の導電率を有する導電材料によって５μｍ以下の膜厚で被覆されたものであることが好ましい。
また、本発明の正極合材において、導電材［Ｃ］における１Ｓ／ｃｍ以上の導電率を有する導電材料の含有量は、０．５重量％以上であることが好ましい。
In the present manufacturing method, the activated carbon is coated by adjusting the type and amount of the conductive material, the type and amount of the solvent and dispersion medium, the immersion time of the activated carbon in the conductive material solution and dispersion, stirring conditions, and the temperature in each process. Film thickness of the conductive material can be controlled. For example, in order to increase the film thickness of the conductive material, the temperature is first increased to increase the concentration of the conductive material solution, and as the concentration of the conductive material solution decreases with the coating of activated carbon, saturation of the conductive material occurs. It is good to gradually lower the temperature while being careful not to exceed the concentration.
In the positive electrode mixture material of the present invention, the conductive material [C] is preferably coated with a conductive material having a conductivity of 1 S / cm or more and a thickness of 5 μm or less.
Further, in the positive electrode composite material of the present invention, the content of the conductive material having a conductivity of 1 S / cm or more in the conductive material [C] is preferably 0.5% by weight or more.
本発明の正極合材において、硫黄及び／又はその放電生成物［Ａ］の含有量は、硫黄及び／又はその放電生成物［Ａ］、イオン伝導性物質［Ｂ］、並びに、導電材［Ｃ］の合計量の４０重量％以上であることが好ましい。
硫黄及び／又はその放電生成物［Ａ］成分の含有量が硫黄及び／又はその放電生成物［Ａ］、イオン伝導性物質［Ｂ］、並びに、導電材［Ｃ］の合計量の４０重量％未満では、硫黄当たりの充放電容量は大きくなるものの、正極合材当たりの充放電容量には限界があり、電池とした際に十分な性能に達しない可能性がある。
また、イオン伝導性物質［Ａ］成分の含有量は、硫黄及び／又はその放電生成物［Ａ］、イオン伝導性物質［Ｂ］、並びに、導電材［Ｃ］の合計量の７０重量％以下であることが好ましい。硫黄及び／又はその放電生成物［Ａ］成分の含有量が硫黄及び／又はその放電生成物［Ａ］、イオン伝導性物質［Ｂ］、並びに、導電材［Ｃ］の合計量の７０重量％を超えると、イオン伝導性物質［Ｂ］及び導電材［Ｃ］の正極合材に占める割合が小さくなり、充放電効率が低下することがある。
In the positive electrode composite material of the present invention, the content of sulfur and / or its discharge product [A] is sulfur and / or its discharge product [A], ion conductive material [B], and conductive material [C] It is preferable that it is 40 weight% or more of the total amount of].
The content of sulfur and / or its discharge product [A] component is 40% by weight of the total of sulfur and / or its discharge product [A], ion conductive material [B], and conductive material [C] Below, although the charge / discharge capacity per sulfur will become large, the charge / discharge capacity per positive electrode composite material has a limit, and when it is set as a battery, sufficient performance may not be reached.
In addition, the content of the ion conductive substance [A] component is 70% by weight or less of the total amount of sulfur and / or its discharge product [A], the ion conductive substance [B], and the conductive material [C] Is preferred. The content of sulfur and / or its discharge product [A] component is 70% by weight of the total of sulfur and / or its discharge product [A], ion conductive material [B], and conductive material [C] The ratio of the ion conductive material [B] and the conductive material [C] in the positive electrode mixture decreases, and the charge and discharge efficiency may decrease.
本発明の正極合材において、硫黄及び／又はその放電生成物［Ａ］、イオン伝導性物質［Ｂ］、並びに、導電材［Ｃ］の各成分の重量基準による含有割合（成分［Ａ］：成分［Ｂ］：成分［Ｃ］）は、４０〜７０：２０〜５５：５〜２０であることが好ましい。
イオン伝導性物質［Ｂ］の含有割合が上記範囲より小さいと、正極へ移動可能なリチウムイオンの量が減少し十分な充放電容量が得られないことがあり、一方、上記範囲より多いと、導電材［Ｃ］の正極合材に占める割合が小さくなり、正極合材当たりの充放電容量が小さくなることがある。
また、導電材［Ｃ］の含有割合が上記範囲より小さいと、正極へ移動可能な電子の量が減少し十分な充放電容量が得られないことがあり、一方、上記範囲より多いと、イオン伝導性物質［Ｂ］の正極合材に占める割合が小さくなり、正極合材当たりの充放電容量が小さくなることがある。
In the positive electrode composite material of the present invention, the content ratio of sulfur and / or its discharge product [A], ion conductive substance [B], and each component of conductive material [C] on a weight basis (component [A]: Component [B]: Component [C]) is preferably 40 to 70: 20 to 55: 5 to 20.
When the content ratio of the ion conductive substance [B] is smaller than the above range, the amount of lithium ions transferable to the positive electrode may be reduced and a sufficient charge / discharge capacity may not be obtained. The proportion of the conductive material [C] in the positive electrode mixture may be small, and the charge / discharge capacity per positive electrode mixture may be small.
In addition, if the content ratio of the conductive material [C] is smaller than the above range, the amount of electrons movable to the positive electrode may be reduced, and sufficient charge and discharge capacity may not be obtained. The proportion of the conductive substance [B] in the positive electrode mixture may be small, and the charge / discharge capacity per positive electrode mixture may be small.
本発明の正極合材は、必要に応じて、バインダー、溶媒等の任意成分を含んでいても良い。 The positive electrode mixture material of the present invention may optionally contain optional components such as a binder and a solvent.
＜バインダー＞
上記バインダーとしては、特に限定されないが、熱可塑性樹脂や熱硬化性樹脂等を用いることができ、例えば、ポリエチレン、ポリプロピレン、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）、スチレンブタジエンゴム、テトラフルオロエチレン−ヘキサフルオロエチレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−クロロトリフルオロエチレン共重合体、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ樹脂）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、フッ化ビニリデン−ペンタフルオロプロピレン共重合体、プロピレン−テトラフルオロエチレン共重合体、エチレン−クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体、フッ化ビニリデン−パーフルオロメチルビニルエーテル−テトラフルオロエチレン共重合体、エチレン−アクリル酸共重合体、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリアクリル酸リチウム、ポリメタクリル酸、ポリメタクリル酸ナトリウム、ポリメタクリル酸リチウム等が挙げられる。
これらのバインダーは、単独で使用しても良いし、２種以上を併用しても良い。
<Binder>
The binder is not particularly limited, but thermoplastic resins, thermosetting resins and the like can be used. For example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene rubber, Tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer Vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE resin), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoroethylene Oropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl Examples thereof include vinyl ether-tetrafluoroethylene copolymers, ethylene-acrylic acid copolymers, polyacrylic acids, sodium polyacrylates, lithium polyacrylates, polymethacrylic acids, sodium polymethacrylates, lithium polymethacrylates and the like.
These binders may be used alone or in combination of two or more.
本発明の正極合材が上記バインダーを混合して得られたものである場合、その含有量は、特に限定されないが、上記正極合材中０．０１〜１０重量％であることが好ましい。 When the positive electrode mixture of the present invention is obtained by mixing the above-mentioned binder, the content thereof is not particularly limited, but preferably 0.01 to 10% by weight in the above-mentioned positive electrode mixture.
＜溶媒＞
上記溶媒を混合して得られた正極合材では、正極合材層を作製しやすくなる。上記溶媒は、正極合材層を作製する際、乾燥により除去される。
上記溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ―ジメチルアミノプロピルアミン、ジエチレントリアミン等のアミン系溶媒、テトラヒドロフラン等のエーテル系溶媒、メチルエチルケトン等のケトン系溶媒、酢酸メチル等のエステル系溶媒、ジメチルアセトアミド、１−メチル−２−ピロリドン等のアミド系溶媒、トルエン、キシレン、ｎ−ヘキサン、シクロヘキサン等の炭化水素系溶媒等が挙げられる。
これらの溶媒は、単独で使用しても良いし、２種以上を併用しても良い。
<Solvent>
In the positive electrode mixture obtained by mixing the above solvents, the positive electrode mixture layer can be easily manufactured. The said solvent is removed by drying, when producing a positive electrode compound material layer.
The solvent is not particularly limited, and examples thereof include amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine, ether solvents such as tetrahydrofuran, ketone solvents such as methyl ethyl ketone, and ester solvents such as methyl acetate Amide solvents such as dimethylacetamide and 1-methyl-2-pyrrolidone; hydrocarbon solvents such as toluene, xylene, n-hexane and cyclohexane; and the like.
These solvents may be used alone or in combination of two or more.
本発明の正極合材が上記溶媒を混合して得られたものである場合、その含有量は、特に限定されないが、上記正極合材中１０〜９９重量％であることが好ましい。 When the positive electrode mixture of the present invention is obtained by mixing the above solvents, the content thereof is not particularly limited, but it is preferably 10 to 99% by weight in the above-mentioned positive electrode mixture.
＜正極合材の作製方法＞
本発明の正極合材は、上記硫黄及び／又はその放電生成物［Ａ］、上記イオン伝導性物質［Ｂ］、並びに、上記導電材［Ｃ］、更には、必要に応じてバインダー、溶媒等の任意成分を混合することにより得ることができる。
これらを混合する方法としては、特に限定されず従来公知の方法を用いることができるが、例えば、遊星ボールミル（フリッチュ社製）、ハイブリダイゼーションシステム（奈良機械製作所社製）、コスモス（川崎重工業社製）、メカノフュージョンシステム（ホソカワミクロン社製）、ノビルタＮＯＢ（ホソカワミクロン社製）、メカノミル（岡田精工社製）、シータコンポーザ（徳寿工作所社製）、ナノソニックミル（井上製作所社製）、ニーダー（井上製作所社製）、スーパーマスコロイダー（増幸産業社製）、ナノメック・リアクター（テクノアイ社製）、コーネルデスパ（浅田鉄工所社製）、プラネタリミキサ（浅田鉄工所社製）、ミラクルＫＣＫ（浅田鉄工所社製）、振動ミル（マツボー社製）等を用いて混合する方法等が挙げられる。
<Method of producing positive electrode mixture>
The positive electrode mixture material of the present invention comprises the above sulfur and / or its discharge product [A], the above ion conductive material [B], the above conductive material [C], and, optionally, a binder, a solvent, etc. Can be obtained by mixing the optional components of
The method of mixing these is not particularly limited, and a conventionally known method can be used. For example, a planetary ball mill (manufactured by Fritsch), a hybridization system (manufactured by Nara Machinery Co., Ltd.), Cosmos (manufactured by Kawasaki Heavy Industries, Ltd.) ), Mechanofusion system (made by Hosokawa Micron), Nobilta NOB (made by Hosokawa Micron), Mechano mill (made by Okada Seiko), Theta composer (made by Tokuju Works Co., Ltd.), Nanosonic mill (made by Inoue Seisakusho), kneader (Inoue) Manufactured by Mfg. Co., Ltd., Super Mass Colloider (Masuko Sangyo Co., Ltd.), Nanomek Reactor (manufactured by Techno Eye), Cornell Despa (manufactured by Asada Iron Works, Ltd.), Planetary Mixer (manufactured by Asada Iron Works, Inc.), Miracle KCK (Asada Iron Works) Manufactured by Toshisha Co., Ltd., vibration mill (manufactured by Matsubo Co., Ltd.), etc. It is.
上記正極合材の作製においては、各成分を混合した後、加熱処理を行っても良い。
この理由は、正極合材が含有する硫黄及び／又はその放電生成物［Ａ］、イオン伝導性物質［Ｂ］、並びに、導電材［Ｃ］の接触界面を強固にすることができ、界面抵抗を低減することができるからである。
上記加熱処理は、特に限定されないが、例えば、アルゴン、窒素、空気等の雰囲気下、８０〜２５０℃、好ましくは１００〜２００℃の条件で、１秒間〜１０時間行うことができる。
上記加熱処理は、従来公知の加熱装置を用いて行えばよく、具体的には、例えば、定温乾燥機、送風乾燥機、減圧乾燥機、赤外線乾燥機等を用いて行えば良い。
In preparation of the said positive electrode compound material, you may heat-process, after mixing each component.
The reason for this is that the contact interface between sulfur contained in the positive electrode mixture and / or its discharge product [A], ion conductive material [B], and conductive material [C] can be strengthened, and interface resistance can be achieved. It is because it can reduce.
The heat treatment is not particularly limited, and can be performed, for example, under an atmosphere of argon, nitrogen, air, or the like at 80 to 250 ° C., preferably 100 to 200 ° C., for 1 second to 10 hours.
The heat treatment may be performed using a conventionally known heating device, and specifically, for example, may be performed using a constant temperature dryer, a blower dryer, a reduced pressure dryer, an infrared dryer, or the like.
＜＜全固体型リチウム硫黄電池＞＞
次に、本発明の全固体型リチウム硫黄電池について説明する。
本発明の全固体型リチウム硫黄電池は、本発明の正極合材を含む正極合材層、固体電解質層、負極及び集電体を備える。
<< All solid state lithium sulfur battery >>
Next, the all-solid-state lithium-sulfur battery of the present invention will be described.
The all solid lithium-sulfur battery of the present invention comprises a positive electrode mixture layer containing the positive electrode mixture of the present invention, a solid electrolyte layer, a negative electrode and a current collector.
本明細書において、「全固体型」とは、電解質として高分子固体電解質及び／又は無機固体電解質を用いたものであり、負極、固体電解質層及び正極合材層に実質的に溶媒を含有しないものをいう。
なお、本明細書において、「実質的に溶媒を含有しない」とは、溶媒が微量に残存しても良いことを意味する。
In the present specification, "all solid type" refers to using a solid polymer electrolyte and / or an inorganic solid electrolyte as the electrolyte, and the negative electrode, the solid electrolyte layer and the positive electrode mixture layer substantially do not contain a solvent. I say something.
In the present specification, "substantially free of solvent" means that a small amount of solvent may remain.
本発明の全固体型リチウム硫黄電池は、例えば、負極、固体電解質層、正極合
材層が順に積層され、その両側に集電体（負極集電体、正極集電体）が配置された構造とすることが出来る。
以下、集電体（負極集電体、正極集電体）、負極、固体電解質層、正極合材層のそれぞれについて順に説明する。
The all-solid-state lithium-sulfur battery of the present invention has, for example, a structure in which a negative electrode, a solid electrolyte layer, and a positive electrode mixture layer are sequentially stacked, and current collectors (negative electrode current collector, positive electrode current collector) are disposed on both sides thereof. It can be done.
Hereinafter, each of the current collector (negative electrode current collector, positive electrode current collector), negative electrode, solid electrolyte layer, and positive electrode mixture layer will be described in order.
＜集電体＞
上記集電体としては、特に限定されないが、例えば、Ａｌ、Ｃｕ、Ｎｉ、ステンレス等を用いることができる。
負極集電体としては、リチウムと合金を作り難い点、及び、薄膜に加工しやすい点から、Ｃｕを用いることが好ましい。
正極集電体としては、薄膜に加工しやすく、安価であるという点でＡｌを用いることが好ましい。
<Current collector>
Although it does not specifically limit as said collector, For example, Al, Cu, Ni, stainless steel etc. can be used.
It is preferable to use Cu as the negative electrode current collector from the viewpoint of being difficult to form an alloy with lithium and being easy to process into a thin film.
As the positive electrode current collector, it is preferable to use Al in terms of being easy to process into a thin film and being inexpensive.
＜負極＞
上記負極としては、リチウムイオンを吸蔵放出する材料を負極活物質として含んでいるものであれば、特に限定されるものではない。ここで、リチウムイオンを吸蔵放出する材料としては、例えば、金属リチウム、リチウム合金、金属酸化物、金属硫化物、リチウムイオンを吸蔵放出する炭素質物質等が挙げられる。
上記リチウム合金としては、例えば、アルミニウム、シリコン、スズ、マグネシウム、インジウム、カルシウム等とリチウムとの合金等が挙げられる。
上記金属酸化物としては、例えば、スズ酸化物、ケイ素酸化物、リチウムチタン酸化物、ニオブ酸化物、タングステン酸化物等が挙げられる。
上記金属硫化物としては、例えば、スズ硫化物やチタン硫化物等が挙げられる。
上記リチウムイオンを吸蔵放出する炭素質物質としては、例えば、黒鉛、コークス、メソフェーズピッチ系炭素繊維、球状炭素、樹脂焼成炭素等が挙げられる。
<Negative electrode>
The negative electrode is not particularly limited as long as it contains a material capable of absorbing and desorbing lithium ions as a negative electrode active material. Here, examples of the material that occludes and releases lithium ions include metal lithium, lithium alloys, metal oxides, metal sulfides, and carbonaceous materials that occlude and release lithium ions.
Examples of the lithium alloy include an alloy of aluminum, silicon, tin, magnesium, indium, calcium and the like, and lithium.
Examples of the metal oxide include tin oxide, silicon oxide, lithium titanium oxide, niobium oxide, tungsten oxide and the like.
Examples of the metal sulfide include tin sulfide and titanium sulfide.
Examples of the carbonaceous material that occludes and releases lithium ions include graphite, coke, mesophase pitch carbon fibers, spherical carbon, resin-fired carbon, and the like.
上記負極を得る方法としては、特に限定されないが、上記リチウムイオンを吸蔵放出する材料をプレスする方法、上記リチウムイオンを吸蔵放出する材料と溶媒とを含む負極前駆体分散液を負極集電体に塗布、乾燥後プレスする方法等が挙げられる。
上記負極前駆体分散液に含まれる溶媒としては、上述の正極合材に用いられるものと同様のものを用いることができる。
なお、溶媒は負極前駆体分散液の塗布を助けるために使用され、塗布後は乾燥により除去される。
The method of obtaining the negative electrode is not particularly limited. However, a method of pressing the material that occludes and releases lithium ions, a negative electrode precursor dispersion containing the material that occludes and releases lithium ions and a solvent A method of pressing after application and drying may, for example, be mentioned.
As a solvent contained in the said negative electrode precursor dispersion liquid, the thing similar to what is used for the above-mentioned positive mix can be used.
The solvent is used to aid the application of the negative electrode precursor dispersion, and is removed by drying after the application.
＜固体電解質層＞
固体電解質層としては、高分子固体電解質及び／又は無機固体電解質からなるものが挙げられる。
上記無機固体電解質としては、例えば、導電率が０．１ｍＳ／ｃｍ以上である固体電解質を用いても良い。上記固体電解質の具体例としては、導電率が０．１ｍＳ／ｃｍ以上であるものであれば特に限定されないが、リチウム塩、リチウム硫化物、リチウム酸化物、リチウム窒化物等が挙げられる。
<Solid electrolyte layer>
As a solid electrolyte layer, what consists of a polymeric solid electrolyte and / or an inorganic solid electrolyte is mentioned.
As the inorganic solid electrolyte, for example, a solid electrolyte having a conductivity of 0.1 mS / cm or more may be used. Specific examples of the solid electrolyte are not particularly limited as long as the conductivity is 0.1 mS / cm or more, and examples include lithium salt, lithium sulfide, lithium oxide, lithium nitride and the like.
上記固体電解質は、リチウム塩、リチウム硫化物又はこれらの組合せであることが好ましい。その理由は、導電率が高く、粒界抵抗が小さいためである。 The solid electrolyte is preferably a lithium salt, a lithium sulfide or a combination thereof. The reason is that the conductivity is high and the grain boundary resistance is small.
上記リチウム塩としては、特に限定されないが、例えば、ＬｉＢＨ４、ＬｉＩ等が挙げられる。
上記リチウム硫化物としては、特に限定されないが、例えば、上記ＰｘＳｙと複合化されたもの、具体的には、上記Ｌｉ２ＳとＰｘＳｙとの複合化物等が挙げられ、また、Ｌｉ２Ｓ及びＰｘＳｙとともに、さらにＧｅＳ２、ＳｉＳ２、Ｌｉ３ＰＯ４、Ｌｉ４ＳｉＯ４等を複合化したものであっても良い。
上記リチウム酸化物としては、特に限定されないが、例えば、Ｌｉ２Ｏ、Ｌｉ２Ｏ２等が挙げられる。
上記リチウム窒化物としては、特に限定されないが、例えば、Ｌｉ３Ｎ等が挙げられる。
これらの固体電解質は、単独で用いても良いし、２種以上を併用しても良い。
The lithium salt is not particularly limited, and examples thereof include LiBH 4 and LiI.
The lithium sulfide is not particularly limited, and examples thereof include those complexed with the above P x S y , specifically, complex compounds of the above Li 2 S and P x S y , etc. In addition to Li 2 S and P x S y , GeS 2 , SiS 2 , Li 3 PO 4 , Li 4 SiO 4 or the like may be further complexed.
As the lithium oxide is not particularly limited, for example, Li 2 O, Li 2 O 2 and the like.
As the lithium nitride is not particularly limited, for example, Li 3 N and the like.
These solid electrolytes may be used alone or in combination of two or more.
上記無機固体電解質からなる固体電解質層は、例えば、上記固体電解質を加圧成形する方法、上記固体電解質を溶媒に分散させた後塗布・乾燥させる方法等により得ることができる。
上記固体電解質を加圧成形する方法としては、特に限定されないが、例えば、負極集電体と正極集電体とで固体電解質を挟み込んでプレスする方法、加圧成形機の治具でプレスする方法等が挙げられる。
上記固体電解質を溶媒に分散させた後塗布・乾燥させる方法により固体電解質層を得る場合には、乾燥後の固体電解質層を上記と同様の方法でプレスしても良い。
上記固体電解質を分散させる溶媒としては、上述の正極合材に用いられるものと同様のものを用いることができる。
これらの方法により固体電解質層を得る際、固体電解質層の界面抵抗の低減、及び、緻密性の向上を目的に、任意のタイミングで加熱処理を行っても良い。
また、上記高分子固体電解質からなる固体電解質層としては、例えば、過塩素酸リチウムやリチウムビストリフルオロメタンスルホニルアミド等のリチウム塩を含むポリエチレンオキシド系ポリマー等が挙げられる。
The solid electrolyte layer composed of the inorganic solid electrolyte can be obtained, for example, by a method of pressure-molding the solid electrolyte, a method of dispersing the solid electrolyte in a solvent and then coating and drying.
The method of pressure-molding the solid electrolyte is not particularly limited. For example, the method of sandwiching and pressing the solid electrolyte between the negative electrode current collector and the positive electrode current collector, and the method of pressing with a jig of a pressure molding machine Etc.
When the solid electrolyte layer is obtained by dispersing the solid electrolyte in a solvent and then applying and drying it, the dried solid electrolyte layer may be pressed by the same method as described above.
As the solvent for dispersing the solid electrolyte, the same one as used in the above-mentioned positive electrode mixture can be used.
When obtaining a solid electrolyte layer by these methods, you may heat-process at arbitrary timing for the purpose of reduction of the interfacial resistance of a solid electrolyte layer, and a densification improvement.
Moreover, as a solid electrolyte layer which consists of said high molecular solid electrolyte, the polyethylene oxide type polymer etc. which contain lithium salts, such as lithium perchlorate and lithium bis trifluoromethane sulfonylamide, are mentioned, for example.
＜正極合材層＞
上記正極合材層は、例えば、正極集電体に上記正極合材を担持させる方法、上記正極合材を加圧成形する方法等により得ることができる。
正極集電体に上記正極合材を担持させる方法としては、特に限定されないが、例えば、正極合材を加圧成形する方法、有機溶媒等を用いてペースト化した正極合材を正極集電体に塗布、乾燥後プレスするなどして固着する方法等が挙げられる。
正極合材を加圧成形する方法としては、特に限定されないが、例えば、固体電解質層と正極集電体との間に正極合材を挟み込んでプレスする方法、加圧成形機の治具でプレスする方法等が挙げられる。
正極合材を正極集電体に塗布する方法としては、特に限定されないが、例えば、スリットダイ塗工法、スクリーン塗工法、カーテン塗工法、ナイフ塗工法、グラビア塗工法、静電スプレー法等が挙げられる。
これらの方法により正極合材層を得る際、正極合材層の界面抵抗の低減、及び、緻密性の向上を目的に、任意のタイミングで加熱処理を行っても良い。
<Positive electrode material layer>
The positive electrode mixture layer can be obtained, for example, by a method of supporting the positive electrode mixture on a positive electrode current collector, a method of pressure forming the positive electrode mixture, or the like.
The method of supporting the positive electrode mixture on the positive electrode current collector is not particularly limited. For example, a method of pressure-molding the positive electrode mixture, a positive electrode current collector made of the positive electrode mixture pasteted using an organic solvent or the like And the like, and a method of fixing by applying, drying and pressing, etc. may be mentioned.
The method of pressure forming the positive electrode mixture is not particularly limited. For example, a method of sandwiching and pressing the positive electrode mixture between the solid electrolyte layer and the positive electrode current collector, pressing with a jig of a pressure forming machine And the like.
The method for applying the positive electrode mixture to the positive electrode current collector is not particularly limited, and examples thereof include slit die coating method, screen coating method, curtain coating method, knife coating method, gravure coating method, electrostatic spray method and the like. Be
When obtaining the positive electrode mixture layer by these methods, heat treatment may be performed at any timing for the purpose of reducing the interfacial resistance of the positive electrode mixture layer and improving the compactness.
上記全固体型リチウム硫黄電池は、上述の負極集電体、負極、固体電解質層、正極合材層、正極集電体のほか、セパレータ等を有していても良い。
上記全固体型リチウム硫黄電池の形状は、特に限定されないが、例えば、コイン型、ボタン型、シート型、積層型、円筒型、偏平型、角型等が挙げられる。
The all solid lithium-sulfur battery may have a separator or the like in addition to the above-mentioned negative electrode current collector, negative electrode, solid electrolyte layer, positive electrode mixture layer, positive electrode current collector.
The shape of the all-solid-state lithium-sulfur battery is not particularly limited, and examples thereof include coin-type, button-type, sheet-type, laminate-type, cylindrical, flat-type, and square-type.
＜全固体型リチウム硫黄電池の作製方法＞
上記全固体型リチウム硫黄電池の作製方法は、特に限定されないが、例えば、以下の方法等が挙げられる。
まず、負極集電体と正極集電体とで固体電解質を挟み込んでプレスし、固体電解質層を作製する。次に、固体電解質層の片側に正極合材を堆積し、その両端を集電体（固体電解質層側に負極集電体、正極合材側に正極集電体）で挟み込んでプレスし、固体電解質層の一方の面に正極合材層と正極集電体とを積層し、固体電解質層のもう一方の面に負極集電体を積層する。最後に、一旦、負極集電体を取り除き、固体電解質層の正極合材層側と反対側に負極を入れ、さらに、負極側に負極集電体を入れてプレスし、固体電解質層の他方の面に負極と負極集電体とを積層する。また、上記のように一層ずつプレスしても良いし、二層以上を堆積させて、複数層をまとめてプレスして積層させても良い。このような方法により、全固体型リチウム硫黄電池を作製することができる。
<Production method of all solid state lithium sulfur battery>
Although the manufacturing method of the said all-solid-type lithium sulfur battery is not specifically limited, For example, the following method etc. are mentioned.
First, a solid electrolyte is sandwiched and pressed between a negative electrode current collector and a positive electrode current collector to produce a solid electrolyte layer. Next, the positive electrode mixture is deposited on one side of the solid electrolyte layer, and both ends thereof are sandwiched and pressed with a current collector (a negative electrode current collector on the solid electrolyte layer side and a positive electrode current collector on the positive electrode mixture side) The positive electrode mixture layer and the positive electrode current collector are laminated on one side of the electrolyte layer, and the negative electrode collector is laminated on the other side of the solid electrolyte layer. Finally, the negative electrode current collector is once removed, the negative electrode is placed on the side opposite to the positive electrode mixture layer side of the solid electrolyte layer, and then the negative electrode current collector is placed on the negative electrode side and pressed. The negative electrode and the negative electrode current collector are laminated on the surface. In addition, one layer may be pressed as described above, or two or more layers may be deposited, and a plurality of layers may be pressed together and stacked. By such a method, an all-solid-state lithium-sulfur battery can be produced.
＜全固体型リチウム硫黄電池の用途＞
上記全固体型リチウム硫黄電池の用途としては、特に限定されないが、例えば、ハイブリッド自動車や電気自動車等、高いエネルギー密度が要求される電気製品に好適に用いることができる。
<Applications of all solid state lithium sulfur battery>
Although it does not specifically limit as a use of the said all-solid-state lithium sulfur battery, For example, it can use suitably for the electrical products which high energy density is requested | required, such as a hybrid vehicle and an electric vehicle.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例のみに限定されるものではない。 EXAMPLES The present invention will be described by way of examples below, but the present invention is not limited to these examples.
１．イオン伝導性物質［Ｂ］の調製
（合成例１）
Ｌｉ２ＳとＰ２Ｓ５を６０：４０のモル比となるようにＬｉ２Ｓ（フルウチ化学社製）を２８４ｍｇ、Ｐ２Ｓ５（アルドリッチ社製）を９１６ｍｇ秤量し、乳鉢で混合したものを遊星ボールミル（Ｆｒｉｌｓｃｈ社製ｐｒｅｍｉｕｍ ｌｉｎｅ Ｐ−７、公転半径０．０７ｍ、自転半径０．０２３５ｍ、自転と公転の比＝−２）にて５ｍｍのジルコニアボール約１８０ｇとともに９０ｍｌのポットにて自転速度２５０ｒｐｍ、公転速度５００ｒｐｍ（自転と逆回転）で１０時間処理することで、リン重量比が０．２１３のイオン伝導性物質［Ｂ］を得た。得られたイオン伝導性物質［Ｂ］の導電率は、０．０２５ｍＳ／ｃｍであった。
1. Preparation of Ion Conducting Substance [B] (Synthesis Example 1)
284 mg of Li 2 S (Furuuchi Chemical Co., Ltd.) and 916 mg of P 2 S 5 (manufactured by Aldrich) so that the molar ratio of Li 2 S to P 2 S 5 is 60:40, and mixed in a mortar In a 90 ml pot with approximately 180 g of 5 mm zirconia balls in a planetary ball mill (premium line P-7 manufactured by Frilsch, revolution radius 0.07 m, rotation radius 0.0235 m, rotation to revolution ratio = -2) The ion conductive material [B] having a phosphorus weight ratio of 0.213 was obtained by treatment at 250 rpm and a revolution speed of 500 rpm (revolution and reverse rotation) for 10 hours. The conductivity of the obtained ion conductive material [B] was 0.025 mS / cm.
２．導電材［Ｃ］の調製
活性炭として活性炭Ａ（関西熱化学社製、比表面積３０００ｍ２／ｇ）、及び、活性炭Ｂ（クラレ社製、比表面積２０００ｍ２／ｇ）の炭素材料を使用した。
活性炭を被覆するための導電材料Ｃとして、ポリ‐３，４‐エチレンジオキシチオフェン／ポリスチレンスルホネート（ＰＥＤＯＴ／ＰＳＳ）の水分散液であるＣｌｅｖｉｏｓ™ ＰＨ５００（ヘレウス社製、１％ＰＥＤＯＴ／ＰＳＳ水分散液）、及び、導電材料Ｄとしてポリアニリン（ＰＡｎ、三陽色素社製）をＮ−メチルホルムアミドに１％溶解した溶液を用いた。
2. Preparation of Conductive Material [C] A carbon material of activated carbon A (manufactured by Kansai Thermochemicals, specific surface area of 3000 m 2 / g) and activated carbon B (manufactured by Kuraray, specific surface area of 2000 m 2 / g) was used as activated carbon.
Clevios ™ an aqueous dispersion of poly-3,4-ethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS) as conductive material C for coating activated carbon; PH 500 (Heraeus, 1% PEDOT / PSS) A water dispersion liquid) and, as the conductive material D, a solution in which 1% of polyaniline (PAn, manufactured by Sanyo Dyes Co., Ltd.) was dissolved in N-methylformamide was used.
（合成例２）
４２５ｍｇの活性炭Ａと７．５ｇの導電材料Ｃ（固形分７５ｍｇ）、２．０ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た（ＰＥＤＯＴ／ＰＳＳは固形分の１５％）。
(Composition example 2)
425 mg of activated carbon A, 7.5 g of conductive material C (75 mg solids), 2.0 g of water and 0.5 g of N-methylformiamide are stirred with a stirrer for 3 days, after which the solvent is distilled off under reduced pressure The powder obtained was washed with water, and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C] (PEDOT / PSS is 15% of solid content).
（合成例３）
４７５ｍｇの活性炭Ａと２．５ｇの導電材料Ｃ（固形分２５ｍｇ）、７．０ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た（ＰＥＤＯＴ／ＰＳＳは固形分の５％）。
(Composition example 3)
Stir 475 mg of activated carbon A, 2.5 g of conductive material C (solid content 25 mg), 7.0 g of water and 0.5 g of N-methylformiamide with a stirrer for 3 days, and then remove the solvent under reduced pressure. The powder obtained was washed with water, and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C] (PEDOT / PSS is 5% of solid content).
（合成例４）
４９５ｍｇの活性炭Ａと０．５ｇの導電材料Ｃ（固形分５ｍｇ）、９．０ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た（ＰＥＤＯＴ／ＰＳＳは固形分の１％）。
(Composition example 4)
495 mg of activated carbon A, 0.5 g of conductive material C (5 mg of solid content), 9.0 g of water and 0.5 g of N-methylformiamide are stirred with a stirrer for 3 days, after which the solvent is distilled off under reduced pressure. The powder obtained was washed with water, and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C] (PEDOT / PSS is 1% of solid content).
（合成例５）
４９７．５ｍｇの活性炭Ａと０．２５ｇの導電材料Ｃ（固形分２．５ｍｇ）、９．２５ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た（ＰＥＤＯＴ／ＰＳＳは固形分の０．５％）。
(Composition example 5)
497.5 mg of activated carbon A and 0.25 g of conductive material C (solid content 2.5 mg), 9.25 g of water and 0.5 g of N-methylformiamide are stirred with a stirrer for 3 days and then reduced pressure The solvent was distilled off, and the obtained powder was washed with water and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C] (PEDOT / PSS is 0.5% of the solid content).
（合成例６）
４５０ｍｇの活性炭Ｂと５．０ｇの導電材料Ｃ（固形分５０ｍｇ）、４．５ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た（ＰＥＤＯＴ／ＰＳＳは固形分の１０％）。
Synthesis Example 6
Stir 450 mg of activated carbon B, 5.0 g of conductive material C (solid content 50 mg), 4.5 g of water and 0.5 g of N-methylformiamide with a stirrer for 3 days, and then remove the solvent under reduced pressure. The powder obtained was washed with water, and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C] (PEDOT / PSS is 10% of the solid content).
（合成例７）
４７５ｍｇの活性炭Ｂと２．５ｇの導電材料Ｃ（固形分２５ｍｇ）、７．０ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た（ＰＥＤＯＴ／ＰＳＳは固形分の５％）。
Synthesis Example 7
Stir 475 mg of activated carbon B, 2.5 g of conductive material C (solid content 25 mg), 7.0 g of water and 0.5 g of N-methylformiamide with a stirrer for 3 days, and then remove the solvent under reduced pressure. The powder obtained was washed with water, and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C] (PEDOT / PSS is 5% of solid content).
（合成例８）
４８５ｍｇの活性炭Ｂと１．５ｇの導電材料Ｃ（固形分１５ｍｇ）、８．０ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た。（ＰＥＤＯＴ／ＰＳＳは固形分の３％)
Synthesis Example 8
485 mg of activated carbon B, 1.5 g of conductive material C (solid content 15 mg), 8.0 g of water and 0.5 g of N-methylformiamide are stirred with a stirrer for 3 days, after which the solvent is distilled off under reduced pressure. The powder obtained was washed with water and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C]. (3% of solid content of PEDOT / PSS)
（合成例９）
４７５ｍｇの活性炭Ｂと２．５ｇの導電材料Ｄ（固形分２５ｍｇ）、７．０ｇの水及び０．５ｇのＮ−メチルホルミアミドをスターラーで３日間撹拌し、その後、減圧にて溶媒を留去し、得られた粉末を水洗いし、１２０℃で３日間減圧乾燥することで導電材料［Ｃ］を得た（ＰＡｎは固形分の５％）。
３．正極合材の作製
（比較例１）
硫黄及び／又はその放電生成物［Ａ］としての硫黄（アルドリッチ社製）、イオン伝導性物質［Ｂ］として合成例１で得たイオン伝導性物質、及び、導電材［Ｃ］として活性炭Ａを用い、その組成比（重量比）が６０：３０：１０となるように硫黄及び／又はその放電生成物［Ａ］１２０ｍｇ、イオン伝導性物質［Ｂ］６０ｍｇ、導電材［Ｃ］２０ｍｇを秤量し、遊星ボールミル（Ｆｒｉｌｓｃｈ社製ｐｒｅｍｉｕｍ ｌｉｎｅ Ｐ−７、公転半径０．０７ｍ、自転半径０．０２３５ｍ、自転と公転の比＝−２）にて５ｍｍのジルコニアボール約４０ｇとともに４５ｍｌのポットにて公転速度３７０ｒｐｍで４時間混合することにより、全固体型リチウム硫黄電池用の正極合材を得た。
Synthesis Example 9
Stir 475 mg of activated carbon B, 2.5 g of conductive material D (solid content 25 mg), 7.0 g of water and 0.5 g of N-methylformiamide with a stirrer for 3 days, and then remove the solvent under reduced pressure. The powder obtained was washed with water, and dried under reduced pressure at 120 ° C. for 3 days to obtain a conductive material [C] (PAn is 5% of solid content).
3. Preparation of positive electrode mixture (comparative example 1)
Sulfur and / or sulfur (manufactured by Aldrich) as the discharge product [A], the ion conductive material obtained in Synthesis Example 1 as the ion conductive material [B], and activated carbon A as the conductive material [C] 120 mg of sulfur and / or its discharge product [A], 60 mg of ion conductive material [B] and 20 mg of conductive material [C] so that the composition ratio (weight ratio) becomes 60:30:10 The planetary ball speed (premium line P-7 manufactured by Frillsch, orbital radius 0.07 m, rotational radius 0.0235 m, rotation-revolution ratio = -2), revolution speed in a 45 ml pot together with about 40 g of zirconia balls of 5 mm By mixing for 4 hours at 370 rpm, a positive electrode mixture for an all solid lithium-sulfur battery was obtained.
（実施例１）
硫黄及び／又はその放電生成物［Ａ］としての硫黄（アルドリッチ社製）、イオン伝導性物質［Ｂ］として合成例１で得たイオン伝導性物質、及び、導電材［Ｃ］として合成例２の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
Example 1
Sulfur and / or sulfur (manufactured by Aldrich) as the discharge product [A], the ion conductive material obtained in Synthesis Example 1 as the ion conductive material [B], and Synthesis Example 2 as the conductive material [C] A positive electrode mixture was obtained by the same mixing treatment as in Comparative Example 1 except that the above-described conductive material was used.
（比較例２）
導電材［Ｃ］として活性炭Ｂを用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Comparative example 2)
A positive electrode mixture was obtained by the same mixing treatment as in Comparative Example 1 except that activated carbon B was used as the conductive material [C].
（実施例２）
導電材［Ｃ］として合成例３の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Example 2)
A positive electrode mixture was obtained by the same mixing process as in Comparative Example 1 except that the conductive material of Synthesis Example 3 was used as the conductive material [C].
（実施例３）
導電材［Ｃ］として合成例４の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Example 3)
A positive electrode mixture was obtained by the same mixing process as in Comparative Example 1 except that the conductive material of Synthesis Example 4 was used as the conductive material [C].
（実施例４）
導電材［Ｃ］として合成例５の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Example 4)
A positive electrode mixture was obtained by the same mixing process as in Comparative Example 1 except that the conductive material of Synthesis Example 5 was used as the conductive material [C].
（実施例５）
導電材［Ｃ］として合成例６の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Example 5)
A positive electrode mixture was obtained by the same mixing process as in Comparative Example 1 except that the conductive material of Synthesis Example 6 was used as the conductive material [C].
（実施例６）
導電材［Ｃ］として合成例７の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Example 6)
A positive electrode composite material was obtained by the same mixing process as in Comparative Example 1 except that the conductive material of Synthesis Example 7 was used as the conductive material [C].
（実施例７）
導電材［Ｃ］として合成例８の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Example 7)
A positive electrode composite material was obtained by the same mixing process as in Comparative Example 1 except that the conductive material of Synthesis Example 8 was used as the conductive material [C].
（実施例８）
導電材［Ｃ］として合成例９の導電材を用いたこと以外、比較例１と同様の混合処理により正極合材を得た。
(Example 8)
A positive electrode mixture was obtained by the same mixing process as in Comparative Example 1 except that the conductive material of Synthesis Example 9 was used as the conductive material [C].
３．全固体型リチウム硫黄電池の作製
ポリカーボネート製の円筒管治具（内径１０ｍｍΦ、外径２３ｍｍΦ、高さ２０ｍｍ）の下側から負極集電体としてＳＵＳ３０４製の円筒治具（１０ｍｍΦ、高さ１０ｍｍ）を差し込み、ポリカーボネート製の円筒管治具の上側から固体電解質（５Ｌｉ２Ｓ−ＧｅＳ２−Ｐ２Ｓ５を５１０℃で８時間焼成した複合化物）７０ｍｇを入れて、さらに正極集電体としてＳＵＳ３０４製の円筒治具（１０ｍｍΦ、高さ１５ｍｍ）をポリカーボネート製の円筒管治具の上側から差し込んで固体電解質を挟み込み、２００ＭＰａの圧力で３分間プレスすることにより直径１０ｍｍΦ、厚さ約０．６ｍｍの固体電解質層を形成した。
次に、上側から差し込んだＳＵＳ３０４製の円筒治具（正極集電体）を一旦抜き取り、ポリカーボネート製の円筒管内の固体電解質層の上に実施例１〜８及び比較例１〜２で作製した正極合材を６．３ｍｇとなるようにそれぞれ入れ、再び上側からＳＵＳ３０４製の円筒治具（正極集電体）を差し込み、２００ＭＰａの圧力で３分間プレスすることで、直径１０ｍｍΦ、厚さ約０．１ｍｍの正極合材層を形成した。
次に、下側から差し込んだＳＵＳ３０４製の円筒治具（負極集電体）を抜き取り、負極として厚さ０．２５ｍｍのリチウムシート（フルウチ化学社製）を穴あけポンチで直径８ｍｍΦに打ち抜いたものと厚さ０．３ｍｍのインジウムシート（フルウチ化学社製）を穴あけポンチで直径９ｍｍΦに打ち抜いたものを重ねてポリカーボネート製の円筒管治具の下側から入れて、再び下側からＳＵＳ３０４製の円筒治具（負極集電体）を差し込み、８０ＭＰａの圧力で３分間プレスすることでリチウム−インジウム合金負極を形成した。
以上のようにして、下側から順に、負極集電体、リチウム−インジウム合金負極、固体電解質層、正極合材層、正極集電体が積層された全固体型リチウム硫黄電池を作製した。
3. Preparation of all solid lithium-sulfur battery Cylindrical jig made of SUS304 (10 mm 、, height 10 mm) as a negative electrode current collector from the lower side of polycarbonate cylindrical tube jig (inner diameter 10 mm mm, outer diameter 23 mm 高, height 20 mm) Insert 70 mg of a solid electrolyte (a composite of 5Li 2 S-GeS 2 -P 2 S 5 fired at 510 ° C. for 8 hours) from the upper side of a polycarbonate cylindrical jig and insert SUS304 as a positive electrode current collector. A cylindrical jig (10 mm 、, height 15 mm) is inserted from the upper side of a polycarbonate cylindrical jig, a solid electrolyte is sandwiched, and pressed for 3 minutes at a pressure of 200 MPa. An electrolyte layer was formed.
Next, the cylindrical jig made of SUS304 (positive electrode current collector) inserted from the upper side was once taken out, and the positive electrodes prepared in Examples 1 to 8 and Comparative Examples 1 and 2 on the solid electrolyte layer in the cylindrical cylinder made of polycarbonate. The mixed material is put in each of 6.3 mg, and a cylindrical jig (positive electrode current collector) made of SUS304 is inserted again from the upper side, and pressed for 3 minutes at a pressure of 200 MPa. A 1 mm positive electrode mixture layer was formed.
Next, the cylindrical jig (negative electrode current collector) made of SUS304 inserted from the lower side is removed, and a lithium sheet (manufactured by Furuuchi Chemical Co., Ltd.) with a thickness of 0.25 mm is punched out with a punch to a diameter of 8 mm as a negative electrode. A 0.3 mm thick indium sheet (manufactured by Furuuchi Chemical Co., Ltd.) punched out with a punching punch to a diameter of 9 mm 重 ね is piled up and inserted from the lower side of a polycarbonate cylindrical jig, again from the lower side made of SUS304 cylindrical steel The lithium-indium alloy negative electrode was formed by inserting a tool (negative electrode current collector) and pressing for 3 minutes at a pressure of 80 MPa.
As described above, an all-solid-state lithium-sulfur battery in which a negative electrode current collector, a lithium-indium alloy negative electrode, a solid electrolyte layer, a positive electrode mixture layer, and a positive electrode current collector were sequentially stacked from the lower side was produced.
４．評価方法
（充放電試験）
作製した全固体型リチウム硫黄電池を用い、充放電装置（ＡＣＤ−Ｍ０１Ａ、アスカ電子株式会社製）にて、カットオフ電圧をそれぞれ０．５Ｖ（放電）、２．５Ｖ（充電）とし、１．６ｍＡ／ｃｍ２の電流密度で充放電を５サイクル繰り返し、５サイクル目の正極合材重量当たりの放電容量を測定し、表１に示す。
なお、表１には特に示していないが、５サイクル目の正極合材重量当たりの充電容量は、５サイクル目の正極合材重量当たりの放電容量とほぼ同じであった。
表１において、［Ａ］、［Ｂ］及び［Ｃ］はそれぞれ硫黄及び／又はその放電生成物［Ａ］、イオン伝導性物質［Ｂ］及び導電材［Ｃ］を意味する。
4. Evaluation method (charge and discharge test)
The cut-off voltages are respectively set to 0.5 V (discharge) and 2.5 V (charge) in a charge / discharge device (ACD-M01A, manufactured by Aska Electronics Co., Ltd.) using the manufactured all-solid-state lithium-sulfur battery. The charge and discharge were repeated 5 cycles at a current density of 6 mA / cm 2 , and the discharge capacity per weight of the positive electrode mixture at the 5th cycle was measured.
Although not particularly shown in Table 1, the charge capacity per weight of the positive electrode mixture at the fifth cycle was substantially the same as the discharge capacity per weight of the positive electrode mixture at the fifth cycle.
In Table 1, [A], [B] and [C] mean sulfur and / or its discharge product [A], ion conductive material [B] and conductive material [C], respectively.
５．結果と考察
実施例及び比較例で作製した正極合材の評価結果より、電子伝導体として１Ｓ／ｃｍ以上の導電率を有する導電材料で被覆された活性炭に用いることにより、実用的な高電流を流した際の正極合材当たりの充放電容量に優れた全固体型リチウム硫黄電池を得ることができることが明らかとなった。
なお、本発明では、正極合材当たりの充放電容量が３９０ｍＡｈ／ｇ以上であれば良好な正極合材であると考えている。
5. Results and Discussion From the evaluation results of the positive electrode composite prepared in the example and the comparative example, a practical high current can be obtained by using an activated carbon coated with a conductive material having a conductivity of 1 S / cm or more as an electron conductor. It became clear that the all-solid-type lithium-sulfur battery excellent in charge and discharge capacity per positive electrode mixture at the time of flowing can be obtained.
In the present invention, if the charge / discharge capacity per positive electrode mixture is 390 mAh / g or more, it is considered to be a good positive electrode mixture.
Claims (5)
［Ｂ］イオン伝導性物質、並びに、
［Ｃ］１Ｓ／ｃｍ以上の導電率を有する導電性高分子で被覆された、ＢＥＴ比表面積が１０００ｍ２／ｇ以上の活性炭
の成分を含み、成分［Ａ］の含有量が正極合材全体の４０重量％以上である、全固体型リチウム硫黄電池の正極合材層に用いられることを特徴とする正極合材。 [A] Sulfur and / or its discharge product,
[B] ion conductive material, and
[C] A component of activated carbon coated with a conductive polymer having a conductivity of 1 S / cm or more and having a BET specific surface area of 1000 m 2 / g or more, and the content of the component [A] is the entire positive electrode mixture A positive electrode mixture, which is 40% by weight or more and is used in a positive electrode mixture layer of an all solid lithium-sulfur battery.
Positive-electrode mixture layer containing a positive electrode according to claim 1 or 2, solid electrolyte layer, all-solid-state lithium-sulfur battery, characterized in that it comprises a negative electrode and a current collector.
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