JPH08236114A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH08236114A JPH08236114A JP7064975A JP6497595A JPH08236114A JP H08236114 A JPH08236114 A JP H08236114A JP 7064975 A JP7064975 A JP 7064975A JP 6497595 A JP6497595 A JP 6497595A JP H08236114 A JPH08236114 A JP H08236114A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- secondary battery
- positive
- battery
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 17
- 229910052744 lithium Inorganic materials 0.000 title claims description 17
- 239000002905 metal composite material Substances 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 239000011149 active material Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- 229910016997 As2 O3 Inorganic materials 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- -1 LiCF 3 SO 3 Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910012741 LiNi0.5Co0.5O2 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム−遷移金属複
合酸化物を正極活物質とするリチウム二次電池に係わ
り、詳しくは充放電サイクル特性を改善することを目的
とした、正極の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using a lithium-transition metal composite oxide as a positive electrode active material, and more particularly to an improvement of a positive electrode for the purpose of improving charge / discharge cycle characteristics. .
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム二次電池が、水の分解電圧を考慮する必要がな
く、正極活物質を適宜選定することにより高電圧化を達
成することが可能であることから、注目されつつある。2. Description of the Related Art In recent years,
The lithium secondary battery is attracting attention because it is not necessary to consider the decomposition voltage of water and it is possible to achieve higher voltage by appropriately selecting the positive electrode active material.
【０００３】この種の電池の代表的な正極活物質として
は、容易に作製することができるとともに、容量が大き
いことから、ＬｉＶ3 Ｏ8 、ＬｉＦｅＯ2 、ＬｉＮｉＯ
2 、ＬｉＣｏＯ2 、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 など
のリチウム−遷移金属複合酸化物が主に使用されてい
る。As a typical positive electrode active material for this type of battery, LiV 3 O 8 , LiFeO 2 , LiNiO 2 can be easily prepared and have a large capacity.
Lithium-transition metal composite oxides such as 2 , LiCoO 2 , LiMnO 2 and LiMn 2 O 4 are mainly used.
【０００４】しかしながら、リチウム−遷移金属複合酸
化物を正極活物質として使用したリチウム二次電池に
は、充放電サイクル特性が未だ実用上充分満足の行く程
度のものではないという問題がある。これは、リチウム
−遷移金属複合酸化物を正極活物質とする正極は表面の
活性が高いために、正極表面で電解液（非水電解液）が
分解することによるものである。However, the lithium secondary battery using the lithium-transition metal composite oxide as the positive electrode active material has a problem that the charge / discharge cycle characteristics are not yet sufficiently satisfactory for practical use. This is because the positive electrode using the lithium-transition metal composite oxide as the positive electrode active material has high surface activity, and thus the electrolytic solution (nonaqueous electrolytic solution) is decomposed on the positive electrode surface.
【０００５】本発明は、この問題を解決するべくなされ
たものであって、その目的とするところは、正極表面で
の電解液の分解を抑制することにより、充放電サイクル
特性に優れたリチウム二次電池を提供するにある。The present invention has been made to solve this problem, and an object thereof is to suppress decomposition of the electrolytic solution on the surface of the positive electrode, so that lithium lithium having excellent charge-discharge cycle characteristics can be obtained. Next is to provide the battery.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係るリチウム二次電池（本発明電池）は、リ
チウム−遷移金属複合酸化物を活物質とする正極を備え
るリチウム二次電池であって、前記正極の表面に、Ｂｅ
Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ａｌ2
Ｏ3 、ＣｅＯ2 、Ａｓ2 Ｏ3 又はこれらの２種以上の混
合物からなる被膜が形成されていることを特徴とする。A lithium secondary battery according to the present invention (a battery of the present invention) for achieving the above object is a lithium secondary battery having a positive electrode using a lithium-transition metal composite oxide as an active material. On the surface of the positive electrode, Be
O, MgO, CaO, SrO, BaO, ZnO, Al 2
It is characterized in that a coating film formed of O 3 , CeO 2 , As 2 O 3 or a mixture of two or more kinds thereof is formed.
【０００７】上記リチウム−遷移金属複合酸化物として
は、ＬｉＶ3 Ｏ8 、ＬｉＦｅＯ2 、ＬｉＮｉＯ2 、Ｌｉ
ＣｏＯ2 、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 が例示され
る。充放電サイクル特性に特に優れた電池を得る上で、
一般式ＬｉX Ｎｉ1-y Ｃｏy Ｏz （但し、０＜ｘ＜１．
３、０≦ｙ≦１、１．８＜ｚ＜２．２）で表されるリチ
ウム−遷移金属複合酸化物が特に好ましい。Examples of the lithium-transition metal composite oxide include LiV 3 O 8 , LiFeO 2 , LiNiO 2 and Li.
Examples include CoO 2 , LiMnO 2 , and LiMn 2 O 4 . In obtaining a battery with excellent charge / discharge cycle characteristics,
Formula Li X Ni 1-y Co y O z ( where, 0 <x <1.
The lithium-transition metal composite oxide represented by 3, 0 ≦ y ≦ 1, 1.8 <z <2.2) is particularly preferable.
【０００８】上記被膜としては、充放電サイクル特性に
特に優れた電池を得る上で、ＢｅＯ、ＭｇＯ、ＣａＯ、
ＳｒＯ、ＢａＯ、ＺｎＯ又はこれらの２種以上の混合物
からなる被膜が特に好ましい。The above-mentioned coating is used in order to obtain a battery having particularly excellent charge / discharge cycle characteristics, and BeO, MgO, CaO,
A coating made of SrO, BaO, ZnO or a mixture of two or more thereof is particularly preferable.
【０００９】上記被膜を形成するための方法としては、
ＣＶＤ（Chemical Vapor Deposition)、蒸着法、スパッ
タリングが例示される。As a method for forming the above coating,
Examples include CVD (Chemical Vapor Deposition), vapor deposition method, and sputtering.
【００１０】本発明の特徴は、リチウム−遷移金属複合
酸化物を活物質とする正極の表面に特定の被膜を形成し
た点にある。それゆえ、負極材料、非水電解液など、電
池を構成する他の部材については、従来リチウム二次電
池用として提案され、或いは実用されている種々の材料
を特に制限なく用いることが可能である。A feature of the present invention is that a specific coating is formed on the surface of a positive electrode using a lithium-transition metal composite oxide as an active material. Therefore, for the other members constituting the battery, such as the negative electrode material and the non-aqueous electrolyte, various materials conventionally proposed or practically used for lithium secondary batteries can be used without particular limitation. .
【００１１】例えば、負極材料としては、リチウムイオ
ンを電気化学的に吸蔵及び放出することが可能な物質又
は金属リチウムを使用することができる。リチウムイオ
ンを電気化学的に吸蔵及び放出することが可能な物質と
しては、黒鉛、コークス、有機物焼成体等の炭素材料及
びリチウム合金（リチウム−アルミニウム合金、リチウ
ム−鉛合金、リチウム−錫合金）が例示される。For example, as the negative electrode material, a substance capable of electrochemically absorbing and desorbing lithium ions or metallic lithium can be used. Examples of substances capable of electrochemically absorbing and desorbing lithium ions include carbon materials such as graphite, coke, and organic burned materials, and lithium alloys (lithium-aluminum alloys, lithium-lead alloys, lithium-tin alloys). It is illustrated.
【００１２】また、非水電解液の溶媒としては、エチレ
ンカーボネート、ビニレンカーボネート、プロピレンカ
ーボネートなどの高誘電率溶媒や、これらとジエチルカ
ーボネート、ジメチルカーボネート、１，２−ジメトキ
シエタン、１，２−ジエトキシエタン、エトキシメトキ
シエタンなどの低沸点溶媒との混合溶媒が、同溶質とし
ては、ＬｉＰＦ6 、ＬｉＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 、
ＬｉＮ（ＣＦ3 ＳＯ2）2 、ＬｉＢＦ4 、ＬｉＡｓＦ6
が、それぞれ例示される。As the solvent for the non-aqueous electrolyte, a high dielectric constant solvent such as ethylene carbonate, vinylene carbonate or propylene carbonate, or a diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane or 1,2-dicarbonate solvent A mixed solvent with a low-boiling-point solvent such as ethoxyethane or ethoxymethoxyethane, the same solute includes LiPF 6 , LiClO 4 , LiCF 3 SO 3 ,
LiN (CF 3 SO 2 ) 2 , LiBF 4 , LiAsF 6
Are illustrated respectively.
【００１３】[0013]
【作用】正極の表面に特定の金属酸化物からなる被膜が
形成されているので、リチウム−遷移金属複合酸化物と
電解液との反応が起こりにくくなり、正極の表面での電
解液の分解が抑制される。[Function] Since a film made of a specific metal oxide is formed on the surface of the positive electrode, the reaction between the lithium-transition metal composite oxide and the electrolytic solution does not easily occur, and the electrolytic solution is decomposed on the surface of the positive electrode. Suppressed.
【００１４】[0014]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible.
【００１５】（実施例１〜１０） 〔正極〕ＬｉＯＨとＮｉ（ＯＨ）2 Ｃｏ（ＯＨ）2 とを
モル比２：１：１で乳鉢にて混合し、乾燥空気雰囲気下
にて７５０°Ｃで２０時間熱処理し、石川式らいかい乳
鉢にて粉砕して、平均粒径５μｍのＬｉＮｉ0.5 Ｃｏ
0.5 Ｏ2 を得た。(Examples 1 to 10) [Positive electrode] LiOH and Ni (OH) 2 Co (OH) 2 were mixed in a mortar at a molar ratio of 2: 1: 1 and dried at 750 ° C in a dry air atmosphere. Heat treatment for 20 hours, crushed in an Ishikawa Raikai mortar, LiNi 0.5 Co with an average particle size of 5 μm
0.5 O 2 was obtained.
【００１６】次いで、この正極活物質としてのＬｉＮｉ
0.5 Ｃｏ0.5 Ｏ2 と、導電剤としてのアセチレンブラッ
クと、結着剤としてのポリフッ化ビニリデンとを、重量
比９０：６：４で混合して正極合剤を調製し、この正極
合剤を２トン／ｃｍ2 の成型圧で直径２０ｍｍの円盤状
に加圧成型した後、２５０°Ｃで２時間熱処理して正極
（Ａ）を作製した（実施例１〜９）。Then, LiNi as the positive electrode active material is used.
0.5 Co 0.5 O 2 , acetylene black as a conductive agent, and polyvinylidene fluoride as a binder were mixed in a weight ratio of 90: 6: 4 to prepare a positive electrode mixture. A positive electrode (A) was produced by press-molding into a disk having a diameter of 20 mm at a molding pressure of ton / cm 2 and then heat-treating at 250 ° C. for 2 hours (Examples 1 to 9).
【００１７】また、正極活物質としてＬｉＭｎ2 Ｏ4 を
使用したこと以外は上記と同様にして、正極（Ｂ）を作
製した（実施例１０）。A positive electrode (B) was prepared in the same manner as above except that LiMn 2 O 4 was used as the positive electrode active material (Example 10).
【００１８】次いで、下記の条件のスパッタリングを行
って、上記正極（Ａ）又は（Ｂ）の表面に、表１に示す
種々の金属酸化物からなる厚さ約１μｍの被膜を形成し
た。なお、被膜の厚み（金属酸化物の担持量）はスパッ
タリング時間で制御した。Next, sputtering was performed under the following conditions to form a coating of various metal oxides shown in Table 1 having a thickness of about 1 μm on the surface of the positive electrode (A) or (B). The thickness of the coating (the amount of metal oxide supported) was controlled by the sputtering time.
【００１９】（スパッタリングの条件） 真空度：１×１０-7トール(torr) アルゴン（Ａｒ）圧：１×１０-5トール(Sputtering conditions) Degree of vacuum: 1 × 10 −7 torr (torr) Argon (Ar) pressure: 1 × 10 −5 torr
【００２０】[0020]
【表１】 [Table 1]
【００２１】〔負極〕所定の厚みの金属リチウム圧延板
を直径２０ｍｍの円盤状に打ち抜いて負極を作製した。[Negative Electrode] A negative electrode was produced by punching out a rolled metal lithium plate having a predetermined thickness into a disk shape having a diameter of 20 mm.
【００２２】〔非水電解液〕エチレンカーボネートとジ
エチルカーボネートとの体積比１：１の混合溶媒に、六
フッ化リン酸リチウムを１Ｍ（モル／リットル）溶かし
て非水電解液を調製した。[Non-Aqueous Electrolyte Solution] A non-aqueous electrolyte solution was prepared by dissolving 1 M (mol / liter) of lithium hexafluorophosphate in a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1.
【００２３】〔電池の組立〕以上の正負極及び非水電解
液を用いて扁平形の本発明電池ＢＡ１〜ＢＡ１０を組み
立てた（電池寸法：直径２４．０ｍｍ、厚さ３．０ｍ
ｍ）。なお、セパレータとしては、ポリプロピレン製の
微多孔膜を使用し、これに先の非水電解液を含浸させ
た。[Assembly of Battery] Flat batteries of the present invention BA1 to BA10 were assembled using the above positive and negative electrodes and the non-aqueous electrolyte (battery size: diameter 24.0 mm, thickness 3.0 m).
m). As the separator, a polypropylene microporous film was used, which was impregnated with the above non-aqueous electrolyte solution.
【００２４】図１は、作製した本発明電池を模式的に示
す断面図であり、図示の本発明電池Ａは、正極（正極
（Ａ）又は（Ｂ）の表面に特定の金属酸化物からなる被
膜を形成したもの。）１、負極２、これら両電極１，２
を互いに離間するセパレータ３、正極缶４、負極缶５、
正極集電体６、負極集電体７及びポリプロピレン製の絶
縁パッキング８などからなる。FIG. 1 is a sectional view schematically showing the produced battery of the present invention. The illustrated battery A of the present invention comprises a specific metal oxide on the surface of a positive electrode (positive electrode (A) or (B)). With a coating formed thereon) 1, negative electrode 2, both electrodes 1, 2
A separator 3, a positive electrode can 4, a negative electrode can 5,
It is composed of a positive electrode current collector 6, a negative electrode current collector 7, an insulating packing 8 made of polypropylene, and the like.
【００２５】正極１及び負極２は、非水電解液を含浸し
たセパレータ３を介して対向して正負極缶４，５が形成
する電池ケース内に収納されており、正極１は正極集電
体６を介して正極缶４に、又負極２は負極集電体７を介
して負極缶５に接続され、電池内部に生じた化学エネル
ギーを正極缶４及び負極缶５の両端子から電気エネルギ
ーとして外部へ取り出し得るようになっている。The positive electrode 1 and the negative electrode 2 are housed in a battery case formed by the positive and negative electrode cans 4 and 5 facing each other with a separator 3 impregnated with a non-aqueous electrolytic solution interposed therebetween. The positive electrode 1 is a positive electrode current collector. The negative electrode 2 is connected to the positive electrode can 4 via 6 and the negative electrode 2 is connected to the negative electrode can 5 via the negative electrode current collector 7, and the chemical energy generated inside the battery is converted into electrical energy from both terminals of the positive electrode can 4 and the negative electrode can 5. It can be taken out.
【００２６】（比較例１，２）正極の表面に被膜を形成
しなかったこと以外は実施例１〜１０と同様にして、比
較電池ＢＣ１，ＢＣ２を組み立てた。但し、比較電池Ｂ
Ｃ１は、正極（Ａ）を使用したものであり、比較電池Ｂ
Ｃ２は正極（Ｂ）を使用したものである。(Comparative Examples 1 and 2) Comparative batteries BC1 and BC2 were assembled in the same manner as in Examples 1 to 10 except that no coating was formed on the surface of the positive electrode. However, comparative battery B
C1 is the one using the positive electrode (A), and the comparative battery B
C2 uses the positive electrode (B).
【００２７】〔充放電サイクル特性〕本発明電池ＢＡ１
〜ＢＡ１０及び比較電池ＢＣ１，２について、電流密度
１ｍＡ／ｃｍ2 で４．３Ｖまで充電した後、電流密度３
ｍＡ／ｃｍ2 で２．５Ｖまで放電する工程を１サイクル
とする充放電サイクル試験を行い、充放電サイクル特性
を調べた。各電池の１サイクル目の放電容量、４００サ
イクル目の放電容量及び容量維持率〔容量維持率（％）
＝（４００サイクル目の放電容量／１サイクル目の放電
容量）×１００〕を先の表１に示す。[Charge / Discharge Cycle Characteristics] Battery BA1 of the present invention
For ~BA10 and Comparative Batteries BC1,2, was charged at a current density of 1 mA / cm 2 up to 4.3 V, the current density 3
A charging / discharging cycle test in which one cycle includes a step of discharging up to 2.5 V at mA / cm 2 was performed to examine charging / discharging cycle characteristics. Discharge capacity at the first cycle of each battery, discharge capacity at the 400th cycle and capacity retention rate [capacity retention rate (%)
= (Discharge capacity at 400th cycle / discharge capacity at first cycle) × 100] is shown in Table 1 above.
【００２８】表１に示すように、正極表面に特定の被膜
を形成した本発明電池ＢＡ１〜ＢＡ１０は、正極表面に
被膜を形成しなかった比較電池ＢＣ１，ＢＣ２に比べ
て、容量維持率が大きい。特に、正極が同じ本発明電池
ＢＡ１〜ＢＡ９のうちＢＡ４〜ＢＡ９の容量維持率が特
に大きい。このことから、被膜形成材料としてはＢｅ
Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ又はＺｎＯが特に
好ましいことが分かる。また、本発明電池ＢＡ９と本発
明電池ＢＡ１０との比較から、正極活物質としては、Ｌ
ｉＭｎ2 Ｏ4 よりもＬｉＮｉ0.5 Ｃｏ0.5 Ｏ2 に代表さ
れる式ＬｉX Ｎｉ1-y Ｃｏy Ｏz （但し、０＜ｘ＜１．
３、０≦ｙ≦１、１．８＜ｚ＜２．２）で表されるリチ
ウム−遷移金属複合酸化物を使用することが好ましいこ
とが分かる。As shown in Table 1, the batteries BA1 to BA10 of the present invention having a specific coating formed on the surface of the positive electrode have a larger capacity retention rate than the comparative batteries BC1 and BC2 having no coating formed on the surface of the positive electrode. . Particularly, among the batteries BA1 to BA9 of the present invention having the same positive electrode, BA4 to BA9 have a particularly large capacity retention rate. Therefore, Be is used as the film forming material.
It turns out that O, MgO, CaO, SrO, BaO or ZnO are particularly preferred. Further, from the comparison between the battery BA9 of the present invention and the battery BA10 of the present invention, as the positive electrode active material, L
The formula Li X Ni 1-y Co y O z represented by LiNi 0.5 Co 0.5 O 2 rather than iMn 2 O 4 (where 0 <x <1.
It is understood that it is preferable to use the lithium-transition metal composite oxide represented by 3, 0 ≦ y ≦ 1, 1.8 <z <2.2).
【００２９】上記実施例では、リチウム−遷移金属複合
酸化物としてＬｉＮｉ0.5 Ｃｏ0.5Ｏ2 又はＬｉＭｎ2
Ｏ4 を使用したが、本発明は、種々のリチウム−遷移金
属複合酸化物を正極活物質とするリチウム二次電池に適
用し得るものである。In the above embodiment, LiNi 0.5 Co 0.5 O 2 or LiMn 2 was used as the lithium-transition metal composite oxide.
Although O 4 is used, the present invention can be applied to a lithium secondary battery using various lithium-transition metal composite oxides as a positive electrode active material.
【００３０】また、上記実施例では、本発明を扁平形の
リチウム二次電池に適用する場合を例に挙げて説明した
が、本発明電池の形状に特に制限はない。Further, in the above embodiment, the case where the present invention is applied to the flat type lithium secondary battery has been described as an example, but the shape of the battery of the present invention is not particularly limited.
【００３１】[0031]
【発明の効果】本発明電池は、充電時に正極の表面で非
水電解液の分解が起こりにくいので、充放電サイクル特
性に優れる。INDUSTRIAL APPLICABILITY The battery of the present invention is excellent in charge / discharge cycle characteristics because the non-aqueous electrolyte is unlikely to decompose on the surface of the positive electrode during charging.
【図１】実施例で組み立てた扁平形のリチウム二次電池
の断面図である。FIG. 1 is a cross-sectional view of a flat type lithium secondary battery assembled in an example.
１ 正極 ２ 負極 ３ セパレータ 1 Positive electrode 2 Negative electrode 3 Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koji Nishio 2-5-5 Keihan Hondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Toshihiko Saito 2-chome, Keihanhondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd.
Claims (3)
する正極を備えるリチウム二次電池において、前記正極
の表面に、ＢｅＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、
ＺｎＯ、Ａｌ2 Ｏ3 、ＣｅＯ2 、Ａｓ2 Ｏ3 又はこれら
の２種以上の混合物からなる被膜が形成されていること
を特徴とするリチウム二次電池。1. A lithium secondary battery comprising a positive electrode using a lithium-transition metal composite oxide as an active material, wherein the surface of the positive electrode is BeO, MgO, CaO, SrO, BaO,
A lithium secondary battery having a coating film formed of ZnO, Al 2 O 3 , CeO 2 , As 2 O 3 or a mixture of two or more thereof.
する正極を備えるリチウム二次電池において、前記正極
の表面に、ＢｅＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、
ＺｎＯ又はこれらの２種以上の混合物からなる被膜が形
成されていることを特徴とするリチウム二次電池。2. A lithium secondary battery comprising a positive electrode using a lithium-transition metal composite oxide as an active material, wherein BeO, MgO, CaO, SrO, BaO, on the surface of the positive electrode.
A lithium secondary battery having a coating formed of ZnO or a mixture of two or more thereof.
ＬｉX Ｎｉ1-y Ｃｏy Ｏz （但し、０＜ｘ＜１．３、０
≦ｙ≦１、１．８＜ｚ＜２．２）で表されるものである
請求項１又は２記載のリチウム二次電池。3. The lithium-transition metal composite oxide has the formula Li X Ni 1-y Co y O z (where 0 <x <1.3,0
The lithium secondary battery according to claim 1 or 2, which is represented by ≦ y ≦ 1, 1.8 <z <2.2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06497595A JP3172388B2 (en) | 1995-02-27 | 1995-02-27 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06497595A JP3172388B2 (en) | 1995-02-27 | 1995-02-27 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08236114A true JPH08236114A (en) | 1996-09-13 |
| JP3172388B2 JP3172388B2 (en) | 2001-06-04 |
Family
ID=13273567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06497595A Expired - Fee Related JP3172388B2 (en) | 1995-02-27 | 1995-02-27 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3172388B2 (en) |
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| WO2005124899A1 (en) * | 2004-06-22 | 2005-12-29 | Matsushita Electric Industrial Co., Ltd. | Secondary battery and method for producing same |
| JP2006114256A (en) * | 2004-10-12 | 2006-04-27 | Toyota Motor Corp | Positive electrode for secondary battery and use thereof |
| JP2006302880A (en) * | 2005-03-23 | 2006-11-02 | Matsushita Electric Ind Co Ltd | Lithium ion secondary battery and manufacturing method thereof |
| US7879494B2 (en) | 2005-03-23 | 2011-02-01 | Panasonic Corporation | Lithium ion secondary battery and manufacturing method therefor |
| US8236449B2 (en) | 2005-07-11 | 2012-08-07 | Panasonic Corporation | Lithium ion secondary battery with improved electrode stability and safety |
| JP2006261132A (en) * | 2006-05-17 | 2006-09-28 | Nichia Chem Ind Ltd | Positive electrode active material for lithium secondary battery and method for producing the same |
| CN100418256C (en) * | 2006-07-28 | 2008-09-10 | 中国科学院成都有机化学有限公司 | ZnO coated surface spinel type LiMnO positive electrode material and its preparation method |
| JP2008277087A (en) * | 2007-04-27 | 2008-11-13 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery and its manufacturing method |
| EP2028704A1 (en) | 2007-07-11 | 2009-02-25 | Toda Kogyo Corporation | Process for producing composite cathode active material for non-aqueous electrolyte secondary cell |
| JP2009064715A (en) * | 2007-09-07 | 2009-03-26 | Toyota Motor Corp | Positive electrode body and lithium secondary battery using the same |
| US9105926B2 (en) | 2009-07-24 | 2015-08-11 | Sony Corporation | Positive electrode active material, positive electrode, and nonaqueous electrolyte cell |
| US20110143204A1 (en) * | 2010-10-04 | 2011-06-16 | Ford Global Technologies, Llc | Lithium-Containing Electrode Material for Electrochemical Cell Systems |
| US10476100B2 (en) * | 2010-10-04 | 2019-11-12 | Ford Global Technologies, Llc | Lithium-containing electrode material for electrochemical cell systems |
| US8685573B2 (en) | 2011-05-30 | 2014-04-01 | Hitachi Maxell, Ltd. | Cathode active material and lithium ion rechargeable battery using the material |
| CN102332577A (en) * | 2011-09-21 | 2012-01-25 | 东莞新能源科技有限公司 | Lithium ion battery and anode material thereof |
| WO2014068969A1 (en) * | 2012-10-31 | 2014-05-08 | 三洋電機株式会社 | Nonaqueous electrolyte secondary cell |
| US9478802B2 (en) | 2012-10-31 | 2016-10-25 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| CN104603991A (en) * | 2012-10-31 | 2015-05-06 | 三洋电机株式会社 | Nonaqueous electrolyte secondary cell |
| WO2014112329A1 (en) * | 2013-01-15 | 2014-07-24 | 株式会社豊田自動織機 | Positive electrode for lithium ion secondary batteries and lithium ion secondary battery |
| JP2014137848A (en) * | 2013-01-15 | 2014-07-28 | Toyota Industries Corp | Positive electrode for lithium ion secondary battery and lithium ion secondary battery |
| KR20150106883A (en) * | 2013-01-17 | 2015-09-22 | 소니 주식회사 | Active material for secondary batteries, electrode for secondary batteries, secondary battery, battery pack, electric vehicle, electrical energy storage system, electric tool, and electronic device |
| CN104919630A (en) * | 2013-01-17 | 2015-09-16 | 索尼公司 | Active material for secondary battery, electrode for secondary battery, secondary battery, battery pack, electric vehicle, power storage system, electric tool, and electronic device |
| JP2014157812A (en) * | 2013-01-17 | 2014-08-28 | Sony Corp | Active material for secondary cell, electrode for secondary cell, secondary cell, battery pack, electric vehicle, electric power storage system, power tool, and electronic apparatus |
| US9899670B2 (en) | 2013-01-17 | 2018-02-20 | Murata Manufacturing Co., Ltd. | Secondary battery-use active material, secondary battery-use electrode, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus |
| WO2014112420A1 (en) * | 2013-01-17 | 2014-07-24 | ソニー株式会社 | Active material for secondary batteries, electrode for secondary batteries, secondary battery, battery pack, electric vehicle, electrical energy storage system, electric tool, and electronic device |
| WO2014156116A1 (en) * | 2013-03-28 | 2014-10-02 | 三洋電機株式会社 | Positive electrode for nonaqueous-electrolyte secondary battery, method for manufacturing positive electrode for nonaqueous-electrolyte secondary battery, and nonaqueous-electrolyte secondary battery |
| JPWO2014156116A1 (en) * | 2013-03-28 | 2017-02-16 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery positive electrode, non-aqueous electrolyte secondary battery manufacturing method and non-aqueous electrolyte secondary battery |
| US20170110734A1 (en) * | 2014-04-02 | 2017-04-20 | Zeon Corporation | Slurry for lithium ion secondary battery positive electrode-use, method for producing slurry for lithium ion secondary battery positive electrode-use, method for producing positive electrode for lithium ion secondary battery-use, and lithium ion secondary battery |
| JPWO2015151529A1 (en) * | 2014-04-02 | 2017-04-13 | 日本ゼオン株式会社 | Slurry for lithium ion secondary battery positive electrode, method for producing slurry for lithium ion secondary battery positive electrode, method for producing positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| WO2015151529A1 (en) * | 2014-04-02 | 2015-10-08 | 日本ゼオン株式会社 | Slurry for positive electrode of lithium ion secondary cell, production method for slurry for positive electrode of lithium ion secondary cell, production method for positive electrode of lithium ion secondary cell, and lithium ion secondary cell |
| US10566628B2 (en) | 2014-04-02 | 2020-02-18 | Zeon Corporation | Slurry for lithium ion secondary battery positive electrode-use, method for producing slurry for lithium ion secondary battery positive electrode-use, method for producing positive electrode for lithium ion secondary battery-use, and lithium ion secondary battery |
| KR20160010296A (en) * | 2014-07-17 | 2016-01-27 | 삼성전자주식회사 | Cathode for lithium ion secondary battery, and lithium ion secondary battery |
| CN105576215A (en) * | 2016-03-02 | 2016-05-11 | 合肥国轩高科动力能源有限公司 | A kind of surface modification method of positive electrode material of lithium ion battery |
| US10741828B2 (en) | 2016-07-05 | 2020-08-11 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material including lithium cobaltate coated with lithium titanate and magnesium oxide |
| US11043660B2 (en) | 2016-07-05 | 2021-06-22 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material including lithium cobaltate coated with lithium titanate and magnesium oxide |
| US12308421B2 (en) | 2016-09-12 | 2025-05-20 | Semiconductor Energy Laboratory Co., Ltd. | Electrode and power storage device comprising graphene compound |
| US11094927B2 (en) | 2016-10-12 | 2021-08-17 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material particle and manufacturing method of positive electrode active material particle |
| JP2019535503A (en) * | 2016-11-14 | 2019-12-12 | ライラック ソリューションズ，インク． | Lithium extraction using coated ion exchange particles |
| US11806641B2 (en) | 2016-11-14 | 2023-11-07 | Lilac Solutions, Inc. | Lithium extraction with coated ion exchange particles |
| JP2023024975A (en) * | 2016-11-14 | 2023-02-21 | ライラック ソリューションズ，インク． | Lithium extraction with coated ion exchange particles |
| KR20190141640A (en) | 2016-11-18 | 2019-12-24 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20220036926A (en) | 2016-11-18 | 2022-03-23 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20200074939A (en) | 2016-11-18 | 2020-06-25 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20200096475A (en) | 2016-11-18 | 2020-08-12 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20230080388A (en) | 2016-11-18 | 2023-06-07 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20200058373A (en) | 2016-11-18 | 2020-05-27 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20190141638A (en) | 2016-11-18 | 2019-12-24 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20190141639A (en) | 2016-11-18 | 2019-12-24 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20220035359A (en) | 2016-11-18 | 2022-03-22 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | A cathode active material, a method of manufacturing a cathode active material, and a secondary battery |
| KR20230082602A (en) | 2016-11-18 | 2023-06-08 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20250019109A (en) | 2016-11-18 | 2025-02-07 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20190141641A (en) | 2016-11-18 | 2019-12-24 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20180056367A (en) | 2016-11-18 | 2018-05-28 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| EP3547432A4 (en) * | 2016-11-25 | 2020-07-22 | Shenzhen Capchem Technology Co., Ltd. | LITHIUM ION BATTERY |
| US11444274B2 (en) | 2017-05-12 | 2022-09-13 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material particle |
| US12418021B2 (en) | 2017-05-12 | 2025-09-16 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material particle |
| US11489151B2 (en) | 2017-05-12 | 2022-11-01 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material particle |
| US11799080B2 (en) | 2017-05-19 | 2023-10-24 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| US12315923B2 (en) | 2017-05-19 | 2025-05-27 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| US12327867B2 (en) | 2017-05-19 | 2025-06-10 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| US11670770B2 (en) | 2017-06-26 | 2023-06-06 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing positive electrode active material, and secondary battery |
| US12272822B2 (en) | 2017-06-26 | 2025-04-08 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing positive electrode active material, and secondary battery |
| US11794182B2 (en) | 2017-08-02 | 2023-10-24 | Lilac Solutions, Inc. | Lithium extraction with porous ion exchange beads |
| US12374679B2 (en) | 2017-08-02 | 2025-07-29 | Lilac Solutions, Inc. | Ion exchange system for lithium extraction |
| US11253848B2 (en) | 2017-08-02 | 2022-02-22 | Lilac Solutions, Inc. | Lithium extraction with porous ion exchange beads |
| US11865531B2 (en) | 2018-02-28 | 2024-01-09 | Lilac Solutions, Inc. | Ion exchange reactor with particle traps for lithium extraction |
| US11975317B2 (en) | 2018-02-28 | 2024-05-07 | Lilac Solutions, Inc. | Ion exchange reactor with particle traps for lithium extraction |
| CN111564606A (en) * | 2019-02-13 | 2020-08-21 | 深圳市贝特瑞纳米科技有限公司 | Coated multi-element anode material for lithium ion battery, and preparation method and application thereof |
| KR20220122655A (en) | 2019-12-27 | 2022-09-02 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Cathode active material, secondary battery, electronic device |
| US11339457B2 (en) | 2020-01-09 | 2022-05-24 | Lilac Solutions, Inc. | Process for separating undesirable metals |
| KR20220133190A (en) | 2020-01-31 | 2022-10-04 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Cathode active material, secondary battery, electronic device |
| US11594730B2 (en) | 2020-03-30 | 2023-02-28 | Tdk Corporation | Electrode and lithium ion secondary battery |
| US11358875B2 (en) | 2020-06-09 | 2022-06-14 | Lilac Solutions, Inc. | Lithium extraction in the presence of scalants |
| US11964876B2 (en) | 2020-06-09 | 2024-04-23 | Lilac Solutions, Inc. | Lithium extraction in the presence of scalants |
| US11377362B2 (en) | 2020-11-20 | 2022-07-05 | Lilac Solutions, Inc. | Lithium production with volatile acid |
| US11986816B2 (en) | 2021-04-23 | 2024-05-21 | Lilac Solutions, Inc. | Ion exchange devices for lithium extraction |
| US12076662B2 (en) | 2022-03-28 | 2024-09-03 | Lilac Solutions, Inc. | Devices for efficient sorbent utilization in lithium extraction |
| US12370468B2 (en) | 2022-03-28 | 2025-07-29 | Lilac Solutions, Inc. | Lithium extraction enhanced by an alternate phase |
| US12162773B2 (en) | 2022-04-01 | 2024-12-10 | Lilac Solutions, Inc. | Extraction of lithium with chemical additives |
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