JP5641193B2 - All-solid lithium secondary battery - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 39
- 229910052744 lithium Inorganic materials 0.000 title claims description 39
- 239000007787 solid Substances 0.000 title claims description 28
- 239000007784 solid electrolyte Substances 0.000 claims description 91
- 239000007774 positive electrode material Substances 0.000 claims description 61
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 41
- 229910001416 lithium ion Inorganic materials 0.000 claims description 41
- 239000003792 electrolyte Substances 0.000 claims description 40
- 239000007773 negative electrode material Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 21
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 claims description 10
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 claims description 8
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 claims description 8
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 claims description 8
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 claims description 8
- 239000006182 cathode active material Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000007086 side reaction Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910018091 Li 2 S Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 229910003480 inorganic solid Inorganic materials 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 4
- 238000003991 Rietveld refinement Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910012801 Li3PO4—Li2S—P2S5 Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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、全固体リチウム二次電池に関するものである。 The present invention relates to an all-solid lithium secondary battery.
近年、携帯電話・ＰＤＡ・ノートパソコンなどの高機能化に伴い、長時間使用が可能であり、且つ小型・軽量で、安全性の高い二次電池が強く要望されている。かかる要望に応える二次電池として、他の二次電池に比べて、高いエネルギー密度を有するリチウム二次電池が多用されている。 In recent years, there has been a strong demand for a secondary battery that can be used for a long time, is small in size and light in weight, and has high safety, with an increase in functionality of a mobile phone, a PDA, a notebook personal computer, and the like. As a secondary battery that meets such demands, lithium secondary batteries having a higher energy density than other secondary batteries are frequently used.
しかし、従来から使用されてきた可燃性の有機溶媒を含むリチウム二次電池は過充電時や濫用時に液漏れや発火の惧れがある。そのため、電池の高エネルギー密度化に伴い、安全性の確保が重要な課題とされてきた。 However, lithium secondary batteries containing flammable organic solvents that have been used in the past have a risk of liquid leakage or ignition during overcharge or abuse. Therefore, ensuring the safety has been an important issue as the energy density of the battery increases.
このような課題を解決する電池として、有機電解液に比べて化学的に安定で且つ液漏れや発火の惧れがない固体電解質を用いた全固体リチウム二次電池の研究開発が鋭意行われている。 Research and development of all-solid-state lithium secondary batteries using solid electrolytes that are chemically stable and have no risk of liquid leakage or ignition compared to organic electrolytes have been conducted as batteries that solve these problems. Yes.
この全固体リチウム二次電池においては、正極集電体、正極材（正極合材）、固体電解質層、負極材（負極合材）、負極集電体が全て固体または固体粉末から成るため、固体／固体間の接触状態の改善が非常に重要となる。すなわち、積層界面での高いリチウムイオン伝導性、電子伝導性を得るためには強い密着性が必要となり、例えば電極活物質粉末や固体電解質粉末を積層して単動プレスやロールプレスによって圧密することにより、電解液を用いたリチウム二次電池に匹敵する高い電池性能を得ることができる。 In this all-solid lithium secondary battery, the positive electrode current collector, the positive electrode material (positive electrode mixture), the solid electrolyte layer, the negative electrode material (negative electrode mixture), and the negative electrode current collector are all made of solid or solid powder. / Improving the contact state between solids is very important. That is, in order to obtain high lithium ion conductivity and electronic conductivity at the laminated interface, strong adhesion is required. For example, electrode active material powder and solid electrolyte powder are laminated and consolidated by single action press or roll press. Thus, high battery performance comparable to a lithium secondary battery using an electrolytic solution can be obtained.
ところで、従来の電解液系電池では電極の空隙に電解液が浸み込むため、電極／電解質間の接触面積については、それほど大きい問題にはならなかった。
そして、全固体リチウム二次電池においても、当然ながら、高出力化が望まれており、このような要望に応えるものとして、正極活物質と結晶性固体電解質との間の緩衝層としてチタンを含む酸化物固体電解質が用いられたものがある。この結晶性固体電解質としては、イオン伝導性が高く、電気化学的な安定性が高い硫化物系固体電解質が用いられている（例えば、特許文献１参照）。
By the way, in the conventional electrolyte solution battery, since the electrolyte solution penetrates into the gaps of the electrodes, the contact area between the electrode and the electrolyte has not been a big problem.
In all solid lithium secondary batteries, of course, higher output is desired, and in order to meet such demand, titanium is included as a buffer layer between the positive electrode active material and the crystalline solid electrolyte. Some oxide solid electrolytes are used. As this crystalline solid electrolyte, a sulfide-based solid electrolyte having high ion conductivity and high electrochemical stability is used (for example, see Patent Document 1).
この硫化物系無機固体電解質を用いた全固体リチウム二次電池においては、硫化物系無機固体電解質と酸化物正極活物質との接触界面において高抵抗層が形成されており、この高抵抗層は電池特性を低下させる原因の一つであるとともに、硫化物系無機固体電解質と酸化物正極活物質との化学ポテンシャルの違いが当該高抵抗層を形成する原因であると言われている。 In the all solid lithium secondary battery using the sulfide inorganic solid electrolyte, a high resistance layer is formed at the contact interface between the sulfide inorganic solid electrolyte and the oxide positive electrode active material. It is said that it is one of the causes for deteriorating battery characteristics, and the difference in chemical potential between the sulfide-based inorganic solid electrolyte and the oxide positive electrode active material is the cause for forming the high resistance layer.
このため、特許文献１においては、酸化物正極活物質表面をリチウムイオン伝導性酸化物で被覆することで、酸化物正極活物質とリチウムイオン伝導性酸化物の化学ポテンシャルを近くして高抵抗層の形成を抑制し、電池特性すなわち充放電性能の向上が図られている。 For this reason, in Patent Document 1, the surface of the oxide positive electrode active material is covered with a lithium ion conductive oxide, thereby bringing the chemical potential of the oxide positive electrode active material and the lithium ion conductive oxide close to each other and the high resistance layer. Thus, the battery characteristics, that is, the charge / discharge performance is improved.
上述した硫化物系無機固体電解質を用いた全固体リチウム二次電池においては、酸化物正極活物質表面をリチウムイオン伝導性酸化物で被覆することで、酸化物正極活物質とリチウムイオン伝導性酸化物の化学ポテンシャルを近くして高抵抗層の形成を抑制するようにしているが、リチウムイオン伝導性酸化物で被覆する工程が増えることになり、製造コストの上昇に繋がるという問題があった。 In the all-solid lithium secondary battery using the sulfide-based inorganic solid electrolyte described above, the oxide positive electrode active material and the lithium ion conductive oxide are coated by covering the surface of the oxide positive electrode active material with a lithium ion conductive oxide. Although the chemical potential of the material is made close to suppress the formation of the high resistance layer, there is a problem in that the number of steps for coating with a lithium ion conductive oxide increases, leading to an increase in manufacturing cost.
そこで、本発明は、製造コストを上昇させることなく充放電性能の向上を図り得る全固体リチウム二次電池を提供することを目的とする。 Then, an object of this invention is to provide the all-solid-state lithium secondary battery which can aim at the improvement of charging / discharging performance, without raising manufacturing cost.
上記課題を解決するため、本発明の全固体リチウム二次電池は、正極材と負極材との間にリチウムイオン伝導性固体電解質層を介在させてなる全固体リチウム二次電池において、
上記正極材を正極活物質とリチウムイオン伝導性固体電解質とから構成するとともに、この正極材における固体電解質として、硫化物系結晶性電解質と硫化物系非晶質電解質との混合物を用いるとともに、正極材に含まれる硫化物系非晶質電解質の割合を、正極材全体に対して１〜１５質量％の範囲となるようにし、
上記リチウムイオン伝導性固体電解質層として硫化物系結晶性電解質を用い、
上記負極材を負極活物質とリチウムイオン伝導性固体電解質とで構成するとともに、この負極材における固体電解質として硫化物系結晶性電解質を用いたものである。
また上記全固体リチウム二次電池における硫化物系結晶性電解質としてＬｉ２Ｓ−Ｐ２Ｓ５を用いるとともに、硫化物系非晶質電解質としてＬｉ３ＰＯ４−Ｌｉ２Ｓ−ＳｉＳ２を用いたものである。
In order to solve the above problems, the all solid lithium secondary battery of the present invention is an all solid lithium secondary battery in which a lithium ion conductive solid electrolyte layer is interposed between a positive electrode material and a negative electrode material.
As well as constituting the cathode material from the cathode active material and the lithium ion conductive solid electrolyte, as a solid electrolyte in the positive electrode, Rutotomoni with a mixture of sulfide-based amorphous electrolyte and sulfide-based crystalline electrolyte, The ratio of the sulfide-based amorphous electrolyte contained in the positive electrode material is in the range of 1 to 15% by mass with respect to the entire positive electrode material,
Using a sulfide-based crystalline electrolyte as the lithium ion conductive solid electrolyte layer,
As well as constituting the negative electrode material in the negative electrode active material and a lithium ion conductive solid electrolyte, Ru der those using a sulfide-based crystalline electrolyte as the solid electrolyte in the negative electrode material.
With use of the Li 2 S-P 2 S 5 as a sulfide-based crystalline electrolyte in upper Symbol all-solid lithium secondary battery or a Li 3 PO 4 -Li 2 S- SiS 2 as a sulfide-based amorphous electrolyte It is what was used.
上記全固体リチウム二次電池によると、正極材として、正極活物質との副反応性は高いがイオン伝導性が良い硫化物系結晶性電解質と、イオン伝導度は少し劣るが正極活物質との副反応性が低い硫化物系非晶質電解質との混合物を用いるようにしたので、従来のように、酸化物正極活物質表面をリチウムイオン伝導性酸化物で被覆する必要がないので、製造コストを上げることなく且つ充放電性能を損なうことのない二次電池を製造することができる。 According to the all-solid-state lithium secondary battery, as the positive electrode material, a sulfide-based crystalline electrolyte that has high side reactivity with the positive electrode active material but good ion conductivity, and the positive electrode active material is slightly inferior in ionic conductivity. Since a mixture with a sulfide-based amorphous electrolyte with low side reactivity is used, it is not necessary to coat the surface of the oxide positive electrode active material with a lithium ion conductive oxide as in the prior art. It is possible to manufacture a secondary battery that does not impair the charge / discharge performance without increasing the battery life.
［実施の形態］
以下、本発明の実施の形態に係る全固体リチウム二次電池について説明する。
この全固体リチウム二次電池は、図１に示すように、正極材（正極合材）４と負極材（負極合材）２との間にリチウムイオン伝導性固体電解質層３が配置されるとともに、正極材４の上記リチウムイオン伝導性固体電解質層３とは反対側の表面に正極集電体５が、また負極材２の上記リチウムイオン伝導性固体電解質層３とは反対側の表面に負極集電体１が、それぞれ積層されたものであり、さらに上記正極材４を正極活物質とリチウムイオン伝導性固体電解質とから構成するとともに、この正極材４におけるリチウムイオン伝導性固体電解質として硫化物系結晶性電解質と硫化物系非晶質電解質との混合物を用い、上記リチウムイオン伝導性固体電解質層３として硫化物系結晶性電解質を用い、上記負極材２を負極活物質とリチウムイオン伝導性固体電解質とで構成するとともに、負極活物質として炭素材料を用い且つ当該負極材２におけるリチウムイオン伝導性固体電解質として硫化物系結晶性電解質を用いたものである。
[Embodiment]
The all-solid lithium secondary battery according to the embodiment of the present invention will be described below.
As shown in FIG. 1, the all solid lithium secondary battery includes a lithium ion conductive solid electrolyte layer 3 disposed between a positive electrode material (positive electrode mixture) 4 and a negative electrode material (negative electrode mixture) 2. The positive electrode current collector 5 is disposed on the surface of the positive electrode material 4 opposite to the lithium ion conductive solid electrolyte layer 3, and the negative electrode material 2 is disposed on the surface opposite to the lithium ion conductive solid electrolyte layer 3. Each of the current collectors 1 is laminated, and the positive electrode material 4 is composed of a positive electrode active material and a lithium ion conductive solid electrolyte, and a sulfide as a lithium ion conductive solid electrolyte in the positive electrode material 4 A mixture of a crystalline electrolyte and a sulfide-based amorphous electrolyte, a sulfide-based crystalline electrolyte as the lithium ion conductive solid electrolyte layer 3, and the negative electrode material 2 as a negative electrode active material and a lithium ion. Together constituting between conductive solid electrolyte, those using a sulfide-based crystalline electrolyte as lithium ion conductive solid electrolyte in and the negative electrode material 2 using a carbon material as an anode active material.
また、上記全固体リチウム二次電池において、正極材４に含まれる硫化物系非晶質電解質の割合を、当該正極材４全体に対して１〜１５質量％（または重量％）の範囲となるようにしたものであり、さらに硫化物系結晶性電解質としてＬｉ２Ｓ−Ｐ２Ｓ５を用いるとともに、硫化物系非晶質電解質としてＬｉ３ＰＯ４−Ｌｉ２Ｓ−ＳｉＳ２を用いたものである。なお、硫化物系非晶質電解質の割合が１％未満であると、結晶性電解質と正極活物質との接触面積が増えて副反応が進行しやすくなり、１５％を超えると、正極に占める非晶質電解質の割合が増えてリチウムイオン伝導性が低下し、放電容量を低下させてしまう。 In the all solid lithium secondary battery, the ratio of the sulfide-based amorphous electrolyte contained in the positive electrode material 4 is in the range of 1 to 15% by mass (or weight%) with respect to the entire positive electrode material 4. Further, Li 2 S—P 2 S 5 is used as a sulfide-based crystalline electrolyte, and Li 3 PO 4 —Li 2 S—SiS 2 is used as a sulfide-based amorphous electrolyte. It is. If the ratio of the sulfide-based amorphous electrolyte is less than 1%, the contact area between the crystalline electrolyte and the positive electrode active material increases, and side reactions tend to proceed. If the ratio exceeds 15%, it accounts for the positive electrode. The proportion of the amorphous electrolyte is increased, the lithium ion conductivity is lowered, and the discharge capacity is lowered.
ここで、本発明を想到するに到った理由を簡単に述べておく。
背景技術の欄で説明した特許文献１においては、硫化物系無機固体電解質と酸化物正極活物質の接触界面において高抵抗層が形成されており、この高抵抗層が電池特性を低下させる原因の一つであると記述されている。
Here, the reason why the present invention has been conceived will be briefly described.
In Patent Document 1 described in the Background Art section, a high resistance layer is formed at the contact interface between the sulfide-based inorganic solid electrolyte and the oxide positive electrode active material, and this high resistance layer is a cause of deterioration in battery characteristics. It is described as one.
そして、本発明者等は、酸化物正極活物質と硫化物系固体電解質の接触界面において副反応が生じていることが高抵抗層生成の原因の一つであると判断した。
すなわち、酸化物正極活物質と硫化物系固体電解質の接触界面において、酸化物正極活物質および硫化物系固体電解質が分解して絶縁体であるＬｉ２Ｓが形成され、これが一種の高抵抗層が形成していると判断した。
The inventors have determined that one of the causes of the generation of the high resistance layer is that a side reaction occurs at the contact interface between the oxide positive electrode active material and the sulfide-based solid electrolyte.
That is, at the contact interface between the oxide positive electrode active material and the sulfide solid electrolyte, the oxide positive electrode active material and the sulfide solid electrolyte are decomposed to form Li 2 S as an insulator, which is a kind of high resistance layer. Was judged to have formed.
一方で、硫化物系非晶質（ガラス状）固体電解質を電極に用いた場合に、副反応が小さくなることを見出したが、充放電性能は低下した。
一般的に、結晶性電解質は優れたリチウムイオン伝導性を有し且つ成形性にも優れていることから、結晶性電解質を電極に用いると充放電特性の優れた電極が得られ、また非晶質電解質は熱安定性が高いことから、非晶質電解質を電極に用いると、保存性能に優れた電極が得られる。
On the other hand, when a sulfide-based amorphous (glassy) solid electrolyte was used for the electrode, the side reaction was found to be small, but the charge / discharge performance was lowered.
In general, since a crystalline electrolyte has excellent lithium ion conductivity and excellent moldability, when the crystalline electrolyte is used as an electrode, an electrode having excellent charge / discharge characteristics can be obtained. Since the electrolyte electrolyte has high thermal stability, when an amorphous electrolyte is used for the electrode, an electrode having excellent storage performance can be obtained.
このことから、硫化物系非晶質固体電解質を電極に用いた場合、熱的な安定性が高いために副反応が小さかったが、結晶性固体電解質に比べてリチウムイオン伝導性が劣るため充放電性能が低下したと考えられる。 Thus, when a sulfide-based amorphous solid electrolyte was used for the electrode, the side reaction was small due to its high thermal stability, but the lithium ion conductivity was inferior to that of the crystalline solid electrolyte. It is considered that the discharge performance has deteriorated.
これらの結果から、本発明者等は、充放電性能を損なわずに保存安定性を向上させるために、副反応が生じる電極層に結晶質と非晶質との二種類の固体電解質を混合する方法が最良であるという知見を得たからである。 From these results, in order to improve storage stability without impairing charge / discharge performance, the present inventors mix two types of solid electrolytes, crystalline and amorphous, in the electrode layer where the side reaction occurs. This is because the knowledge that the method is the best was obtained.
上記全固体リチウム二次電池の構成によると、正極材４として、正極活物質との副反応性は高いがイオン伝導性（イオン伝導度）が良い（優れた）硫化物系結晶性電解質と、イオン伝導度は少し劣るが正極活物質との副反応性が低い硫化物系非晶質電解質とを混合し、且つリチウムイオン伝導性固体電解質層３および負極材４として、イオン伝導性の高いＬｉ２Ｓ−Ｐ２Ｓ５（結晶性電解質）を用いたので、充放電性能を損なうことなく且つ保存特性の優れた二次電池を得ることができる。勿論、従来のように、正極活物質をリチウムイオン伝導性酸化物で被膜する必要がないので、製造コストの上昇を抑制することができる。 According to the configuration of the all solid lithium secondary battery, as the positive electrode material 4, a sulfide-based crystalline electrolyte that has high side reaction with the positive electrode active material but good ion conductivity (ion conductivity) (excellent); Lithium ion conductive solid electrolyte layer 3 and negative electrode material 4 are mixed with a sulfide-based amorphous electrolyte that is slightly inferior in ionic conductivity but low in side reactivity with the positive electrode active material. Since 2 S—P 2 S 5 (crystalline electrolyte) is used, a secondary battery excellent in storage characteristics can be obtained without impairing charge / discharge performance. Of course, unlike the conventional case, it is not necessary to coat the positive electrode active material with a lithium ion conductive oxide, so that an increase in manufacturing cost can be suppressed.
以下、上記全固体リチウム二次電池を具体的に示した実施例１〜４について説明する。これら各実施例においては、全固体リチウム二次電池の構成とともにその製造方法についても説明し、また図１で示した二次電池の構成部材と同一の名称および同一符号を用いて説明する。
［実施例１］
実施例１に係る全固体リチウム二次電池（以下、リチウム二次電池という）は、正極材（正極合材）４と負極材（負極合材）２との間にリチウムイオン伝導性固体電解質層３が配置されるとともに、正極材４のリチウムイオン伝導性固体電解質層３とは反対側の表面に正極集電体５が、また負極材２のリチウムイオン伝導性固体電解質層３とは反対側の表面に負極集電体１が、それぞれ積層されたものである。
Hereinafter, Examples 1 to 4 specifically showing the all solid lithium secondary battery will be described. In each of these examples, the configuration of the all-solid lithium secondary battery and the manufacturing method thereof will be described, and the description will be made using the same names and the same reference numerals as the constituent members of the secondary battery shown in FIG.
[Example 1]
The all solid lithium secondary battery according to Example 1 (hereinafter referred to as a lithium secondary battery) has a lithium ion conductive solid electrolyte layer between a positive electrode material (positive electrode mixture) 4 and a negative electrode material (negative electrode mixture) 2. 3 is disposed, the positive electrode current collector 5 is disposed on the surface of the positive electrode material 4 opposite to the lithium ion conductive solid electrolyte layer 3, and the negative electrode material 2 is opposite to the lithium ion conductive solid electrolyte layer 3. Each of the negative electrode current collectors 1 is laminated on the surface.
上記リチウムイオン伝導性固体電解質層３としては、硫化物系結晶性電解質である０．８０Ｌｉ２Ｓ−０．２０Ｐ２Ｓ５が用いられる。また、この電解質（Ｌｉ２Ｓ−Ｐ２Ｓ５）として、その粉末を目開き５６μｍの篩にかけ、その篩下のものを用いた。 As the lithium ion conductive solid electrolyte layer 3, 0.80Li 2 S-0.20P 2 S 5 which is a sulfide-based crystalline electrolyte is used. Further, as the electrolyte (Li 2 S—P 2 S 5 ), the powder was passed through a sieve having an opening of 56 μm, and the one under the sieve was used.
この固体電解質を４０ｍｇ秤量し、内径１０ｍｍのＳＫＤ（冷間ダイス鋼）製の円筒金型に入れ、１８５ＭＰａで３回加圧成形することにより、リチウムイオン伝導性個体電解質層３を得た。 40 mg of this solid electrolyte was weighed, put into a cylindrical die made of SKD (cold die steel) having an inner diameter of 10 mm, and press-molded three times at 185 MPa to obtain a lithium ion conductive solid electrolyte layer 3.
上記負極材２としては、負極活物質とリチウムイオン伝導性固体電解質との混合物が用いられる。負極活物質としては炭素材料であるグラファイトが用いられるとともに、リチウムイオン伝導性固体電解質としては硫化物系結晶性電解質であるＬｉ２Ｓ−Ｐ２Ｓ５が用いられる。 As the negative electrode material 2, a mixture of a negative electrode active material and a lithium ion conductive solid electrolyte is used. Graphite that is a carbon material is used as the negative electrode active material, and Li 2 S—P 2 S 5 that is a sulfide-based crystalline electrolyte is used as the lithium ion conductive solid electrolyte.
負極活物質であるグラファイトとリチウムイオン伝導性固体電解質（Ｌｉ２Ｓ−Ｐ２Ｓ５）との混合物は、所定の質量比（重量比）、例えば６：４の割合でもって作製される。ここでは、負極活物質と上記固体電解質とを６０ｍｇ：４０ｍｇの割合で秤量し、乳鉢にて十分に混合する。この固体電解質（Ｌｉ２Ｓ−Ｐ２Ｓ５）として、その粉末を目開き５６μｍの篩にかけ、その篩下のものを用いた。 A mixture of graphite as the negative electrode active material and lithium ion conductive solid electrolyte (Li 2 S—P 2 S 5 ) is produced at a predetermined mass ratio (weight ratio), for example, a ratio of 6: 4. Here, the negative electrode active material and the solid electrolyte are weighed at a ratio of 60 mg: 40 mg and sufficiently mixed in a mortar. As this solid electrolyte (Li 2 S—P 2 S 5 ), the powder was passed through a sieve having an opening of 56 μm, and the one under the sieve was used.
ところで、負極材２に用いるリチウムイオン伝導性固体電解質は還元分解されないように、電位窓が広い材料を選択する必要があるが、Ｌｉ２Ｓ−Ｐ２Ｓ５は非常に広い電位窓を有している。 By the way, it is necessary to select a material having a wide potential window so that the lithium ion conductive solid electrolyte used for the negative electrode material 2 is not reductively decomposed. However, Li 2 S—P 2 S 5 has a very wide potential window. ing.
次に、得られた負極材としての混合物を１５ｍｇ秤量して、加圧成形後の固体電解質が入れられた円筒金型に投入し、１８５ＭＰａで３回加圧成形した。
上記正極材４としては、正極活物質と硫化物系非晶質固体電解質と硫化物系結晶性固体電解質との混合物が用いられる。
Next, 15 mg of the obtained mixture as the negative electrode material was weighed, put into a cylindrical mold containing a solid electrolyte after pressure molding, and pressure molded at 185 MPa three times.
As the positive electrode material 4, a mixture of a positive electrode active material, a sulfide-based amorphous solid electrolyte and a sulfide-based crystalline solid electrolyte is used.
また、正極活物質としては、酸素気流中において７００℃で２０時間焼成したＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２（以下、ＮＣＡとも称する）が用いられる。また、硫化物系非晶質（ガラス状）固体電解質としては、例えば０．０１Ｌｉ３ＰＯ４−０．６３Ｌｉ２Ｓ−０．３６ＳｉＳ２が用いられ、硫化物系結晶性固体電解質としては、例えば０．８０Ｌｉ２Ｓ−０．２０Ｐ２Ｓ５が用いられる。これらの固体電解質として、それぞれ目開きが５６μｍの篩にかけ、篩下のものを用いた。 Further, as the positive electrode active material, LiNi 0.8 Co 0.15 Al 0.05 O 2 (hereinafter also referred to as NCA) fired at 700 ° C. for 20 hours in an oxygen stream is used. Further, as the sulfide-based amorphous (glassy) solid electrolyte, for example, 0.01Li 3 PO 4 -0.63Li 2 S-0.36SiS 2 is used, and as the sulfide-based crystalline solid electrolyte, for example, 0.80Li 2 S-0.20P 2 S 5 is used. As these solid electrolytes, sieves having openings of 56 μm were used, and those under the sieve were used.
そして、正極材４は、ＮＣＡとＬｉ３ＰＯ４−Ｌｉ２Ｓ−ＳｉＳ２とＬｉ２Ｓ−Ｐ２Ｓ５とを７：１．５：１．５（質量比）の割合で混合して作製されるが、ＮＣＡと硫化物系非晶質固体電解質であるＬｉ３ＰＯ４−Ｌｉ２Ｓ−ＳｉＳ２とを先に十分に混合した後に、硫化物系結晶性固体電解質であるＬｉ２Ｓ−Ｐ２Ｓ５を追加混合して作製される。 The positive electrode 4, NCA and Li 3 PO 4 -Li 2 S- SiS 2 and Li 2 S-P 2 S 5 and a 7: 1.5: mixed at a ratio of 1.5 (weight ratio) NCA and a sulfide-based amorphous solid electrolyte, Li 3 PO 4 —Li 2 S—SiS 2 , are first mixed thoroughly, and then a sulfide-based crystalline solid electrolyte, Li 2 S. It is prepared by adding mixed -P 2 S 5.
ここでは、まず、正極活物質と硫化物系非晶質固体電解質と硫化物系結晶性固体電解質とをそれぞれ７０ｍｇ：１５ｍｇ：１５ｍｇの割合で秤量し、乳鉢にて十分に混合する。
次に、得られた正極材としての混合物を２０ｍｇ秤量して、加圧成形後の固体電解質−負極材からなる積層部材（積層ペレット）が入れられた円筒金型の固体電解質側に投入し、３７０ＭＰａで３回加圧成形し、そしてこの加圧成形された積層部材を円筒金型から取り出す。
Here, first, the positive electrode active material, the sulfide-based amorphous solid electrolyte, and the sulfide-based crystalline solid electrolyte are weighed in a ratio of 70 mg: 15 mg: 15 mg, and sufficiently mixed in a mortar.
Next, 20 mg of the obtained mixture as the positive electrode material was weighed and charged into the solid electrolyte side of the cylindrical mold in which the laminated member (laminated pellet) composed of the solid electrolyte-negative electrode material after pressure molding was placed, Pressure molding is performed three times at 370 MPa, and the pressure-molded laminated member is taken out from the cylindrical mold.
次に、ＰＥＴ製（ポリエチレンテフタレート）の金型（ダイ）に、チタン（Ｔｉ）の正極集電体５、および正極材４が正極集電体５に接触するように上記積層部材を充填し、その上からチタン（Ｔｉ）の負極集電体１を投入して上下をＳＫＤ製のパンチで挟み、１８５ＭＰａ、３７０ＭＰａ、３７０ＭＰａでもって、順次、加圧成形して積層体を得る。 Next, the laminated member is filled in a PET (polyethylene terephthalate) mold (die) so that the positive electrode current collector 5 of titanium (Ti) and the positive electrode material 4 are in contact with the positive electrode current collector 5. Then, a negative electrode current collector 1 made of titanium (Ti) is inserted from above, and the upper and lower sides are sandwiched between punches made of SKD, and are sequentially pressure-formed with 185 MPa, 370 MPa, and 370 MPa to obtain a laminate.
そして、得られた積層体を電池用セル内に組み込むことにより、全固体リチウム二次電池を得た。
このようにして製造されたリチウム二次電池（つまり、構築直後電池）の初期放電容量および３０日保存後の正極側のＸ線リートベルト解析によるＬｉＮｉＯ２に対するＬｉ２Ｓ検出量並びに３０日保存後の放電容量を調べた結果について、下記の［表１］に示しておく。なお、［表１］には、比較例についてのデータも記載している。
And the all-solid-state lithium secondary battery was obtained by incorporating the obtained laminated body in the battery cell.
The initial discharge capacity of the lithium secondary battery thus manufactured (that is, the battery immediately after construction), the detected amount of Li 2 S for LiNiO 2 by X-ray Rietveld analysis on the positive electrode side after 30 days storage, and after 30 days storage The results of examining the discharge capacity are shown in [Table 1] below. In [Table 1], data on comparative examples are also described.
まず、比較例１について説明する。
比較例１に係る全固体リチウム二次電池の製造方法について説明すると、リチウムイオン伝導性固体電解質層および負極材は、実施例１で説明したものと同一である。
First, Comparative Example 1 will be described.
When the manufacturing method of the all-solid-state lithium secondary battery which concerns on the comparative example 1 is demonstrated, the lithium ion conductive solid electrolyte layer and negative electrode material are the same as what was demonstrated in Example 1. FIG.
正極材としては、正極活物質と硫化物系結晶性固体電解質との混合物が用いられる。正極活物質としては、酸素気流中において７００℃で２０時間焼成したＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２（ＮＣＡ）が用いられている。また、硫化物系結晶性固体電解質としては、例えば０．８０Ｌｉ２Ｓ−０．２０Ｐ２Ｓ５が用いられるとともに、目開きが５６μｍの篩にかけ、篩下のものを用いた。 As the positive electrode material, a mixture of a positive electrode active material and a sulfide-based crystalline solid electrolyte is used. As the positive electrode active material, LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) fired at 700 ° C. for 20 hours in an oxygen stream is used. Further, as the sulfide-based crystalline solid electrolyte, for example, 0.80Li 2 S-0.20P 2 S 5 was used, and a sieve having an opening of 56 μm was used, and the one under the sieve was used.
正極材は、ＮＣＡとＬｉ２Ｓ−Ｐ２Ｓ５とを７：３（質量比）の割合で混合して作製される。ここでは、正極活物質と硫化物系結晶性固体電解質とをそれぞれ７０ｍｇ：３０ｍｇの割合で秤量し、乳鉢にて十分に混合する。 The positive electrode material is produced by mixing NCA and Li 2 S—P 2 S 5 at a ratio of 7: 3 (mass ratio). Here, the positive electrode active material and the sulfide-based crystalline solid electrolyte are weighed at a ratio of 70 mg: 30 mg, respectively, and sufficiently mixed in a mortar.
次に、得られた混合物を２０ｍｇ秤量して、加圧成形後の固体電解質−負極材からなる積層部材（積層ペレット）が入れられた円筒金型の固体電解質側に投入し、３７０ＭＰａで３回加圧成形し、そしてこの加圧成形された積層部材を円筒金型から取り出す。 Next, 20 mg of the obtained mixture was weighed and charged into the solid electrolyte side of a cylindrical mold in which a laminated member (laminated pellet) made of a solid electrolyte-negative electrode material after pressure molding was placed, and three times at 370 MPa. The pressure-molded laminated member is taken out from the cylindrical mold.
次に、ＰＥＴ製の金型（ダイ）に、チタン（Ｔｉ）の正極集電体を配置し、この正極集電体に正極材が接触するように上記積層部材を充填し、チタン（Ｔｉ）の負極集電体１を投入して上下をＳＫＤ製のパンチで挟み、１８５ＭＰａ、３７０ＭＰａ、３７０ＭＰａでもって、順次、加圧成形して積層体を得た。 Next, a titanium (Ti) positive electrode current collector is placed in a PET mold (die), and the laminated member is filled so that the positive electrode material is in contact with the positive electrode current collector. The negative electrode current collector 1 was put in, and the upper and lower parts were sandwiched between punches made of SKD, and were sequentially pressure-formed with 185 MPa, 370 MPa, and 370 MPa to obtain a laminate.
このようにして得られた積層体を電池用セル内に組み込むことにより、リチウム二次電池を製造した。
上述した実施例１と同様に製造されたリチウム二次電池（つまり、構築直後電池）の初期放電容量および３０日保存後の正極側のＸ線リートベルト解析によるＬｉＮｉＯ２に対するＬｉ２Ｓ検出量並びに３０日保存後の放電容量を調べた結果を［表１］に示しておく。比較例１は３０日保存によりＬｉ２Ｓ検出量が増加（副反応が進行）し、その結果、容量の大部分が減少しているため好ましくない。
A lithium secondary battery was manufactured by incorporating the thus obtained laminate into a battery cell.
The initial discharge capacity of the lithium secondary battery manufactured in the same manner as in Example 1 (that is, the battery immediately after construction), the detected amount of Li 2 S with respect to LiNiO 2 by the X-ray Rietveld analysis on the positive electrode side after storage for 30 days, and The results of examining the discharge capacity after 30 days storage are shown in [Table 1]. Comparative Example 1 is not preferable because the amount of Li 2 S detected increases (side reaction proceeds) by storage for 30 days, and as a result, most of the capacity decreases.
次に、比較例２について説明する。
比較例２に係る全固体リチウム二次電池の製造方法について説明すると、リチウムイオン伝導性固体電解質層および負極材については、上述した実施例１（つまり比較例１）と同じである。
Next, Comparative Example 2 will be described.
The manufacturing method of the all-solid lithium secondary battery according to Comparative Example 2 will be described. The lithium ion conductive solid electrolyte layer and the negative electrode material are the same as those in Example 1 (that is, Comparative Example 1) described above.
正極材としては、正極活物質と硫化物系非晶質（ガラス状）固体電解質との混合物が用いられる。正極活物質としては酸素気流中において７００℃で２０時間焼成したＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２（ＮＣＡ）が用いられる。また、硫化物系非晶質固体電解質としては、例えば０．０１Ｌｉ３ＰＯ４−０．６３Ｌｉ２Ｓ−０．３６ＳｉＳ２が用いられ、目開きが５６μｍの篩にかけ、篩下のものを用いた。 As the positive electrode material, a mixture of a positive electrode active material and a sulfide-based amorphous (glassy) solid electrolyte is used. As the positive electrode active material, LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) fired at 700 ° C. for 20 hours in an oxygen stream is used. In addition, as the sulfide-based amorphous solid electrolyte, for example, 0.01Li 3 PO 4 -0.63Li 2 S-0.36SiS 2 is used, and a sieve having a mesh opening of 56 μm is used. .
正極材は、ＮＣＡとＬｉ３ＰＯ４−Ｌｉ２Ｓ−ＳｉＳ２とを７：３（質量比）の割合で混合して作製される。ここでは、正極活物質と硫化物系非晶質固体電解質とをそれぞれ７０ｍｇ：３０ｍｇの割合で秤量し、乳鉢にて十分に混合する。 The positive electrode material is produced by mixing NCA and Li 3 PO 4 —Li 2 S—SiS 2 at a ratio of 7: 3 (mass ratio). Here, the positive electrode active material and the sulfide-based amorphous solid electrolyte are weighed in a ratio of 70 mg: 30 mg, respectively, and sufficiently mixed in a mortar.
次に、得られた混合物を２０ｍｇ秤量して、加圧成形後の固体電解質−負極からなる積層部材が入れられた円筒金型の固体電解質側に投入し、３７０ＭＰａで３回加圧成形し、そしてこの加圧成形された上記積層部材を円筒金型から取り出す。 Next, 20 mg of the obtained mixture was weighed and charged into the solid electrolyte side of the cylindrical mold containing the solid electrolyte-negative electrode laminated member after pressure molding, and pressure molded at 370 MPa three times. The pressure-molded laminated member is taken out from the cylindrical mold.
次に、ＰＥＴ製の金型（ダイ）に、チタン（Ｔｉ）の正極集電体を配置し、この正極集電体に正極材が接触するように上記積層部材を充填し、チタン（Ｔｉ）の負極集電体を投入して上下をＳＫＤ製のパンチで挟み、１８５ＭＰａ、３７０ＭＰａ、３７０ＭＰａでもって、順次、加圧成形して積層体を得た。 Next, a titanium (Ti) positive electrode current collector is placed in a PET mold (die), and the laminated member is filled so that the positive electrode material is in contact with the positive electrode current collector. The negative electrode current collector was put in, and the upper and lower sides were sandwiched between punches made of SKD, and pressure-molded sequentially with 185 MPa, 370 MPa, and 370 MPa to obtain a laminate.
このようにして得られた積層体を電池用セル内に組み込むことにより、リチウム二次電池を製造した。
上述した実施例１と同様に製造されたリチウム二次電池（つまり、構築直後電池）の初期放電容量および３０日保存後の正極側のＸ線リートベルト解析によるＬｉＮｉＯ２に対するＬｉ２Ｓ検出量並びに３０日保存後の放電容量を調べた結果を［表１］に示しておく。比較例２は正極に占める電解質を全て非晶質電解質にしたため副反応は少ないが、リチウムイオン伝導性が低下し容量が出ないため好ましくない。
A lithium secondary battery was manufactured by incorporating the thus obtained laminate into a battery cell.
The initial discharge capacity of the lithium secondary battery manufactured in the same manner as in Example 1 (that is, the battery immediately after construction), the detected amount of Li 2 S with respect to LiNiO 2 by the X-ray Rietveld analysis on the positive electrode side after storage for 30 days, and The results of examining the discharge capacity after 30 days storage are shown in [Table 1]. Comparative Example 2 is not preferable because the electrolyte occupying the positive electrode is all an amorphous electrolyte, so there are few side reactions, but the lithium ion conductivity is lowered and capacity is not generated.
なお、実施例１、比較例１および比較例２の初期充放電はセル加圧力が７８．４ＭＰａのもとで且つ３０℃の恒温槽内で、充電終止電圧４．２Ｖ、放電終止電圧２．５Ｖおよび充放電電流０．１５ｍＡ／ｃｍ２の条件で定電流充放電を行ったものである。
［実施例２〜４］
次に、実施例２〜４について説明する。
The initial charge / discharge of Example 1, Comparative Example 1 and Comparative Example 2 was conducted at a cell pressurization pressure of 78.4 MPa and in a thermostatic chamber at 30 ° C. with a charge end voltage of 4.2 V and a discharge end voltage of 2. A constant current charge / discharge was performed under the conditions of 5 V and a charge / discharge current of 0.15 mA / cm 2 .
[Examples 2 to 4]
Next, Examples 2 to 4 will be described.
実施例２〜４に係る全固体リチウム二次電池は、実施例１と殆ど同じ方法で製造したもので、正極活物質と非晶質固体電解質と結晶性固体電解質との混合比が異なるだけである。すなわち、実施例２については、正極活物質：非晶質固体電解質：結晶性固体電解質の混合比が７０：１：２９（質量比）であり、実施例３については、７０：５：２５（質量比）であり、実施例４については、７０：１０：２０（質量比）である。 The all-solid lithium secondary batteries according to Examples 2 to 4 were manufactured by almost the same method as Example 1, except that the mixing ratio of the positive electrode active material, the amorphous solid electrolyte, and the crystalline solid electrolyte was different. is there. That is, for Example 2, the mixing ratio of positive electrode active material: amorphous solid electrolyte: crystalline solid electrolyte was 70: 1: 29 (mass ratio), and for Example 3, 70: 5: 25 ( Mass ratio), and in Example 4, it is 70:10:20 (mass ratio).
次に、比較例３および比較例４について説明する。
この比較例３に係る全固体リチウム二次電池は、実施例１と殆ど同じ方法で製造したもので、正極活物質と非晶質固体電解質と結晶性固体電解質との混合比が異なるだけである。
Next, Comparative Example 3 and Comparative Example 4 will be described.
The all-solid lithium secondary battery according to Comparative Example 3 was manufactured by almost the same method as in Example 1, and only the mixing ratio of the positive electrode active material, the amorphous solid electrolyte, and the crystalline solid electrolyte was different. .
すなわち、比較例３における正極活物質：非晶質固体電解質：結晶性固体電解質の混合比は、７０：２０：１０（質量比）である。
また、比較例４に係る全固体リチウム二次電池の構成、および固体電解質、正極材の作製方法は実施例１と同じである。
That is, the mixing ratio of positive electrode active material: amorphous solid electrolyte: crystalline solid electrolyte in Comparative Example 3 is 70:20:10 (mass ratio).
The configuration of the all-solid lithium secondary battery according to Comparative Example 4 and the method for producing the solid electrolyte and the positive electrode material are the same as those in Example 1.
負極材としては、負極活物質と硫化物系非晶質固体電解質と硫化物系結晶性固体電解質との混合物が用いられる。
上記負極活物質としては炭素材料であるグラファイトが用いられる。また、硫化物系非晶質固体電解質としては、例えば０．０１Ｌｉ３ＰＯ４−０．６３Ｌｉ２Ｓ−０．３６ＳｉＳ２が用いられ、硫化物系結晶性固体電解質としては、例えば０．８０Ｌｉ２Ｓ−０．２０Ｐ２Ｓ５が用いられる。
As the negative electrode material, a mixture of a negative electrode active material, a sulfide-based amorphous solid electrolyte, and a sulfide-based crystalline solid electrolyte is used.
As the negative electrode active material, graphite which is a carbon material is used. As the sulfide-based amorphous solid electrolyte, for example, 0.01Li 3 PO 4 -0.63Li 2 S-0.36SiS 2 is used, and as the sulfide-based crystalline solid electrolyte, for example, 0.80Li 2 S-0.20P 2 S 5 is used.
これらの固体電解質については、それぞれ目開きが５６μｍの篩にかけ、篩下のものを用いた。
この負極材は、グラファイトとＬｉ３ＰＯ４−Ｌｉ２Ｓ−ＳｉＳ２とＬｉ２Ｓ−Ｐ２Ｓ５とが、６：２：２（質量比）の割合で混合して作製されるが、グラファイトと硫化物系非晶質固体電解質、つまりＬｉ３ＰＯ４−Ｌｉ２Ｓ−ＳｉＳ２を先に十分に混合してから硫化物系結晶性固体電解質、つまりＬｉ２Ｓ−Ｐ２Ｓ５を追加・混合して作製される。
Each of these solid electrolytes was passed through a sieve having an opening of 56 μm, and the one under the sieve was used.
This negative electrode material is produced by mixing graphite, Li 3 PO 4 —Li 2 S—SiS 2 and Li 2 S—P 2 S 5 in a ratio of 6: 2: 2 (mass ratio). First, graphite and a sulfide-based amorphous solid electrolyte, that is, Li 3 PO 4 —Li 2 S—SiS 2 , are thoroughly mixed before the sulfide-based crystalline solid electrolyte, that is, Li 2 S—P 2 S 5 . Made by adding and mixing.
ここでは、負極活物質と硫化物系非晶質固体電解質と硫化物系結晶性固体電解質とをそれぞれ６０ｍｇ：２０ｍｇ：２０ｍｇの割合で秤量し、乳鉢にて十分に混合する。そして、これらの固体電解質、正極材、負極材を用いて実施例１と同様にリチウム二次電池を製造した。 Here, the negative electrode active material, the sulfide-based amorphous solid electrolyte, and the sulfide-based crystalline solid electrolyte are weighed in a ratio of 60 mg: 20 mg: 20 mg, respectively, and sufficiently mixed in a mortar. And the lithium secondary battery was manufactured similarly to Example 1 using these solid electrolyte, positive electrode material, and negative electrode material.
上述した比較例１および比較例２と同様に、製造された二次電池（つまり、構築直後電池）の初期放電容量および３０日保存後の正極側のＸ線リートベルト解析によるＬｉＮｉＯ２に対するＬｉ２Ｓ検出量並びに３０日保存後の放電容量を調べた結果を［表１］に示しておく。比較例３は、比較例１と同様に、３０日保存によりＬｉ２Ｓ検出量が増加（副反応が進行）し、その結果、容量の大部分が減少しているため好ましくない。また、比較例４は充電時に負極が還元分解をしてしまうため、電池構築直後、３０日保存後ともに容量が出ないため好ましくない。 Similar to Comparative Example 1 and Comparative Example 2 described above, the initial discharge capacity of the manufactured secondary battery (that is, the battery immediately after construction) and Li 2 for LiNiO 2 by the X-ray Rietveld analysis on the positive electrode side after 30 days storage [Table 1] shows the results of examining the detected S amount and the discharge capacity after 30 days storage. As in Comparative Example 1, Comparative Example 3 is not preferable because the detected amount of Li 2 S increases (side reaction proceeds) by storage for 30 days, and as a result, most of the capacity decreases. Further, Comparative Example 4 is not preferable because the negative electrode undergoes reductive decomposition at the time of charging, and the capacity does not come out immediately after battery construction and after storage for 30 days.
１ 負極集電体
２ 負極材
３ リチウムイオン伝導性固体電解質層
４ 正極材
５ 正極集電体
DESCRIPTION OF SYMBOLS 1 Negative electrode collector 2 Negative electrode material 3 Lithium ion conductive solid electrolyte layer 4 Positive electrode material 5 Positive electrode collector
Claims (2)
上記正極材を正極活物質とリチウムイオン伝導性固体電解質とから構成するとともに、この正極材における固体電解質として、硫化物系結晶性電解質と硫化物系非晶質電解質との混合物を用いるとともに、正極材に含まれる硫化物系非晶質電解質の割合を、正極材全体に対して１〜１５質量％の範囲となるようにし、
上記リチウムイオン伝導性固体電解質層として硫化物系結晶性電解質を用い、
上記負極材を負極活物質とリチウムイオン伝導性固体電解質とで構成するとともに、この負極材における固体電解質として硫化物系結晶性電解質を用いたことを特徴とする全固体リチウム二次電池。 In an all solid lithium secondary battery in which a lithium ion conductive solid electrolyte layer is interposed between a positive electrode material and a negative electrode material,
As well as constituting the cathode material from the cathode active material and the lithium ion conductive solid electrolyte, as a solid electrolyte in the positive electrode, Rutotomoni with a mixture of sulfide-based amorphous electrolyte and sulfide-based crystalline electrolyte, The ratio of the sulfide-based amorphous electrolyte contained in the positive electrode material is in the range of 1 to 15% by mass with respect to the entire positive electrode material,
Using a sulfide-based crystalline electrolyte as the lithium ion conductive solid electrolyte layer,
An all-solid lithium secondary battery, wherein the negative electrode material is composed of a negative electrode active material and a lithium ion conductive solid electrolyte, and a sulfide-based crystalline electrolyte is used as the solid electrolyte in the negative electrode material.
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