JPH01313861A - Organic electrolyte secondary cell - Google Patents
Organic electrolyte secondary cellInfo
- Publication number
- JPH01313861A JPH01313861A JP63146302A JP14630288A JPH01313861A JP H01313861 A JPH01313861 A JP H01313861A JP 63146302 A JP63146302 A JP 63146302A JP 14630288 A JP14630288 A JP 14630288A JP H01313861 A JPH01313861 A JP H01313861A
- Authority
- JP
- Japan
- Prior art keywords
- organic solvent
- organic
- organic electrolyte
- lithium
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- -1 cyclic carbonate esters Chemical class 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 238000004070 electrodeposition Methods 0.000 abstract 1
- 230000036647 reaction Effects 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明はマンガン酸化物、三酸化モリブデン、五酸化バ
ナジウム、チタン或いはニオブの硫化物やセレン化物な
どの再充電可能な活物質よりなる正極と、リチウム或い
はリチウム合金を活物質とする負極とを備えた有機電解
質二次電池に関するものである。[Detailed description of the invention] (a) Industrial application field The present invention provides a positive electrode made of a rechargeable active material such as manganese oxide, molybdenum trioxide, vanadium pentoxide, titanium or niobium sulfide or selenide. The present invention relates to an organic electrolyte secondary battery comprising: and a negative electrode using lithium or a lithium alloy as an active material.
（ロ）従来の技術
この種電池は放電時にイオンとなって溶出したリチウム
が充電時に金属リチウムとして負極表面に電析するので
あるが、この電析リチウムは表面積の大なる微粒子状で
あるため活性度が高く、そのため有機電解質を構成する
有機溶媒と反応して溶媒を分解し有機電解質を劣化させ
る。それ故、この種電池は充放電サイクル特性が悪いと
いう問題があった。(b) Conventional technology In this type of battery, the lithium eluted as ions during discharge is deposited as metallic lithium on the negative electrode surface during charging, but this electrodeposited lithium is in the form of fine particles with a large surface area, so it is not active. Therefore, it reacts with the organic solvent constituting the organic electrolyte, decomposing the solvent and degrading the organic electrolyte. Therefore, this type of battery has a problem of poor charge/discharge cycle characteristics.
（ハ）発明が解決しようとする課題
本発明は上述せる従来技術の問題点に鑑み、有機電解質
を改良して充放電サイクル特性に優れた４１機電解質二
次電池を提供しようとするものである。(c) Problems to be Solved by the Invention In view of the problems of the prior art described above, the present invention seeks to provide a 41-electrolyte secondary battery with excellent charge/discharge cycle characteristics by improving the organic electrolyte. .
（ニ）課題を解決するための手段
本発明の要旨とするところは、再充電可能な正極と、リ
チウム或いはリチウム合金を活物質とする負極と、混合
有機溶媒に少なくとも一つの溶質を溶解した有機電解質
とを備える有機電解質二次電池において、混合有機溶媒
を構成する一種の有機溶媒としてエチレンカーボネート
を用いることにある。(d) Means for Solving the Problems The gist of the present invention is to provide a rechargeable positive electrode, a negative electrode containing lithium or a lithium alloy as an active material, and an organic compound containing at least one solute dissolved in a mixed organic solvent. In an organic electrolyte secondary battery including an electrolyte, ethylene carbonate is used as a type of organic solvent constituting a mixed organic solvent.
（ホ）作用
混合有機溶媒を構成する一種の有機溶媒としてエチレン
カーボネートを用いると、このエチレンカーボネートと
負極活物質であるリチウムとが反応してリチウム負極表
面にリチウムイオン導電性の薄膜が形成きれ、この薄膜
を介して電池反応は進行すると共に、この薄膜によって
充電時に生成する活性な電析リチウムと有機電解質を構
成する有機溶媒との反応が抑制される。その結果、有機
電解質の劣化が抑えられ充放電サイクル特性の向上が図
れる。(e) Effect When ethylene carbonate is used as a type of organic solvent constituting the mixed organic solvent, this ethylene carbonate and lithium, which is the negative electrode active material, react to form a lithium ion conductive thin film on the surface of the lithium negative electrode. The battery reaction progresses through this thin film, and at the same time, this thin film suppresses the reaction between the active electrodeposited lithium produced during charging and the organic solvent constituting the organic electrolyte. As a result, deterioration of the organic electrolyte is suppressed and charge/discharge cycle characteristics can be improved.
（へ）実施例 以下本発明の実施例について説明する。(f) Example Examples of the present invention will be described below.
実施例１〜１２
正極は化学ＭｎＯ＋８０ ｇとＬｉＯＨ２０ｇとを混合
したものを３７５°Ｃで熱処理して得た活物質８０重量
％に、導電剤としてのアセチレンブラック１０重量％及
び結着剤としてのフッ素樹脂粉末１０重量％を加えて混
合した合剤を加圧成形したものを用い、負極はリチウム
板を所定寸法に打ち抜いたものを用いた。Examples 1 to 12 The positive electrode was made of 80% by weight active material obtained by heat-treating a mixture of 80 g of MnO+ and 20 g of LiOH at 375°C, 10% by weight of acetylene black as a conductive agent, and fluorine as a binder. A mixture prepared by adding and mixing 10% by weight of resin powder was pressure-molded, and the negative electrode was a lithium plate punched to a predetermined size.
そして、電解質として第１表に示すように各種の混合有
機溶媒と溶質とを組み合わせて本発明電池（Ａ）〜（Ｌ
）を作成した。Then, various mixed organic solvents and solutes as shown in Table 1 are used as electrolytes in combination with batteries (A) to (L) of the present invention.
)It was created.
尚、第１表において、サイクル数は充放電電流２ｍＡ、
充電終止電圧４．ＯＶ、放電終止電圧２．ＯＶのサイク
ル条件で充放電を繰り返し、電池容量が９０ｍＡＨ（初
期容量の８０％）以下となった時点で電池寿命とする条
件における充放電回数を示し、又内部抵抗は２０サイク
ル目の内部抵抗値を示４゛。In Table 1, the number of cycles is a charge/discharge current of 2 mA,
Charging end voltage 4. OV, discharge end voltage2. It shows the number of times of charging and discharging under the condition that the battery life is reached when the battery capacity becomes 90mAH (80% of the initial capacity) or less after repeated charging and discharging under OV cycle conditions, and the internal resistance is the internal resistance value at the 20th cycle. Show 4゛.
（以下余白）
第１図は本発明電池の半断面図を示し、（１）、（２）
は正、負極罐であってポリプロピレンよりなる絶縁バッ
キング（３）により隔離されている。(Left below) Figure 1 shows a half cross-sectional view of the battery of the present invention, (1), (2)
are positive and negative electrode containers, which are separated by an insulating backing (3) made of polypropylene.
（４）は正極であり正極罐（１）の内底面に固着せる正
極集電体（５）に圧接されている。（６）は負極であり
負極罐（２）の内底面に固着せる負極集電体（７）に圧
着されている。(4) is a positive electrode, which is pressed into contact with a positive electrode current collector (5) fixed to the inner bottom surface of the positive electrode can (1). (6) is a negative electrode, which is crimped to a negative electrode current collector (7) fixed to the inner bottom surface of the negative electrode housing (2).
（８）はポリプロピレン不織布よりなるセパレータであ
って、有機電解質が含浸きれている。尚、電池寸法は直
径２４ｍ、厚み３．０ｍであり、電池容量は１１０ｍＡ
Ｈである。(8) is a separator made of polypropylene nonwoven fabric, and is completely impregnated with an organic electrolyte. The battery dimensions are 24 m in diameter and 3.0 m in thickness, and the battery capacity is 110 mA.
It is H.
比較例１〜９
溶媒としてエチレンカーボネートを用いず他の溶媒を用
いることを除いて他は実施例１〜１２と同様の電池（い
）〜（す）を作成し、その電池性能を第２表に示す、尚
、電池性能測定条件は第１表と同様である。Comparative Examples 1 to 9 Batteries (i) to (s) were prepared in the same manner as in Examples 1 to 12, except that ethylene carbonate was not used as the solvent and another solvent was used, and the battery performances are shown in Table 2. The conditions for measuring battery performance are the same as those in Table 1.
〈以下余白）
実施例１３〜１４
正極活物質としてＭｎ０ｔに代えてｖ、０６を用いると
共に、有機電解質としてＥＣと１．２Ｄ Ｍ Ｅとの混
合溶媒にＬ ｉＣ１０、を１モル／ｌ溶解したものを用
いた電池（Ｍ）、又ＥＣとＰＣとの混合溶媒にＬｉＣＦ
ｓＳＯｓを１モル／ｌ溶解したものを用いた電池（Ｎ）
を作成した。(Left below) Examples 13 to 14 V,06 was used instead of Mn0t as the positive electrode active material, and 1 mol/l of LiC10 was dissolved in a mixed solvent of EC and 1.2D ME as the organic electrolyte. (M) using LiCF as a mixed solvent of EC and PC
Battery (N) using sSOs dissolved at 1 mol/l
It was created.
実施例１５〜１６
正極活物質としてＭ ｎ Ｏ＋に代えてＭ ｏ Ｓ ｔ
を用いると共に、有機電解質としてＥＣと１．２Ｄ Ｍ
Ｅとの混合溶媒にＬｉＣ１０，を１モル／１溶解した
ものを用いた電池（０）、又ＥＣとＰＣとの混合溶媒に
ＬｆＣＦ、ＳＯ，を１モル／ｌ溶解したものを用いた電
池（Ｐ）を作成した。Examples 15-16 M o S t was used instead of M n O+ as the positive electrode active material
and EC and 1.2D M as organic electrolytes.
A battery (0) using 1 mol/l of LiC10 dissolved in a mixed solvent with E, and a battery using 1 mol/l of LfCF, SO, dissolved in a mixed solvent of EC and PC ( P) was created.
第２図は本発明電池（Ａ）（Ｅ）（Ｍ＞（Ｎ）（０）及
びＣＰ）の放電容量とサイクル数との関係を示す。FIG. 2 shows the relationship between the discharge capacity and the number of cycles for the batteries (A) (E) (M>(N)(0) and CP) of the present invention.
第２図より正極活物質としてＭｎ０ｍを用いるとｖ、ｏ
、ｐびＭ ｏ Ｓ ＊を用いる場合に比してサイクル数
に伴う放電容量の低下率が低いことがわかる。From Figure 2, when Mn0m is used as the positive electrode active material, v, o
It can be seen that the rate of decrease in discharge capacity with the number of cycles is lower than when using , p and M o S *.
（ト）発明の効果
上述した如く、再充電可能な正極と、リチウム或いはリ
チウム合金を活物質とする負極と、混合有機溶媒に少な
くとも一つの溶質を溶解した有機電解質とを備える有機
電解質二次電池において、混合有機溶媒を構成する一種
の有機溶媒としてエチレンカーボネートを用いることに
より、活性な電析リチウムと有機電解質を構成する有機
溶媒との反応が抑制され、有機電解質の劣化を抑えるこ
とができ、充放電サイクル特性の向上が図れるものであ
り、この種電池の用途拡大に資するところ極めて犬であ
る。(g) Effects of the invention As described above, an organic electrolyte secondary battery comprising a rechargeable positive electrode, a negative electrode using lithium or a lithium alloy as an active material, and an organic electrolyte in which at least one solute is dissolved in a mixed organic solvent. By using ethylene carbonate as a type of organic solvent constituting the mixed organic solvent, the reaction between active electrodeposited lithium and the organic solvent constituting the organic electrolyte is suppressed, and deterioration of the organic electrolyte can be suppressed. This makes it possible to improve the charge-discharge cycle characteristics, and is extremely useful in expanding the uses of this type of battery.
第１図は本発明電池の半断面図、第２図は本発明電池の
サイクル特性図を夫々示す。
（１）・・・正極罐、（２）・・・負極罐、（３）・・
・絶縁バッキング、（４）・・・正極、（５）・・・正
極集電体、（６〉・・・負極、（７）・・・負極集電体
、（８）・・・セパレータ。
第２図
寸イフル秋（回）FIG. 1 is a half-sectional view of the battery of the present invention, and FIG. 2 is a cycle characteristic diagram of the battery of the present invention. (1)...Positive electrode can, (2)...Negative electrode can, (3)...
- Insulating backing, (4)...Positive electrode, (5)...Positive electrode current collector, (6>...Negative electrode, (7)...Negative electrode current collector, (8)...Separator. Figure 2: Autumn (time)
Claims (3)
金を活物質とする負極と、混合有機溶媒に少なくとも一
つの溶質を溶解した有機電解質とを備えるものであって
、混合有機溶媒を構成する一種の有機溶媒としてエチレ
ンカーボネートを用いることを特徴とする有機電解質二
次電池。(1) A device comprising a rechargeable positive electrode, a negative electrode using lithium or a lithium alloy as an active material, and an organic electrolyte in which at least one solute is dissolved in a mixed organic solvent, which is a type of mixed organic solvent. An organic electrolyte secondary battery characterized in that ethylene carbonate is used as an organic solvent.
ンカーボネート、γ−プチロラクトンなどの環状炭酸エ
ステル、ジオキソラン及びその誘導体或いはテトラヒド
ロフラン及びその誘導体から選ばれた一種若しくは二種
以上である請求項（１）記載の有機電解質二次電池。(2) Claim (1) in which the other organic solvent constituting the mixed organic solvent is one or more selected from propylene carbonate, cyclic carbonate esters such as γ-butyrolactone, dioxolane and its derivatives, or tetrahydrofuran and its derivatives. ) The organic electrolyte secondary battery described in
（１）記載の有機電解質二次電池。(3) The organic electrolyte secondary battery according to claim (1), wherein the rechargeable positive electrode is a manganese oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63146302A JPH01313861A (en) | 1988-06-14 | 1988-06-14 | Organic electrolyte secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63146302A JPH01313861A (en) | 1988-06-14 | 1988-06-14 | Organic electrolyte secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01313861A true JPH01313861A (en) | 1989-12-19 |
Family
ID=15404605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63146302A Pending JPH01313861A (en) | 1988-06-14 | 1988-06-14 | Organic electrolyte secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01313861A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11977158B2 (en) | 2018-03-23 | 2024-05-07 | Mitsubishi Electric Corporation | Laser radar device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59134568A (en) * | 1983-01-24 | 1984-08-02 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium battery |
| JPS60109182A (en) * | 1983-11-17 | 1985-06-14 | Sanyo Chem Ind Ltd | Secondary battery |
-
1988
- 1988-06-14 JP JP63146302A patent/JPH01313861A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59134568A (en) * | 1983-01-24 | 1984-08-02 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium battery |
| JPS60109182A (en) * | 1983-11-17 | 1985-06-14 | Sanyo Chem Ind Ltd | Secondary battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11977158B2 (en) | 2018-03-23 | 2024-05-07 | Mitsubishi Electric Corporation | Laser radar device |
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