JP3567954B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary battery Download PDFInfo
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- JP3567954B2 JP3567954B2 JP01376896A JP1376896A JP3567954B2 JP 3567954 B2 JP3567954 B2 JP 3567954B2 JP 01376896 A JP01376896 A JP 01376896A JP 1376896 A JP1376896 A JP 1376896A JP 3567954 B2 JP3567954 B2 JP 3567954B2
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- Prior art keywords
- electrolytic solution
- secondary battery
- derivative
- electrolyte
- battery
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- 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.)
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は正極が遷移金属の酸化物又はカルコゲン化物、導電性ポリマー、負極がリチウムを吸蔵放出可能な炭素やリチウム合金、電解液が有機電解液又は高分子固体電解質からなる非水二次電池に関するものである。
【0002】
【従来の技術】
正極が遷移金属の酸化物又はカルコゲン化物、導電性ポリマーから成る非水二次電池の中で、特に正極がLiCoO2やLiNiO2,LiMn2O4等のリチウム電極(Li/Li+)基準で、3.5〜4.3Vで作動する電池がエネルギー密度が高い点で注目され、商品化されている。これらの電池の電解液の溶剤としてはエチレンカーボネート、プロピレンカーボネート、ジエチルカーボネート等の炭酸エステルが一般的に使用されている。
【0003】
【発明が解決しようとする課題】
従来の電池では、特に1サイクル目の充電時に、正極及び負極の表面で電解液の溶剤を構成する前記炭酸エステルの化学的な分解反応が生じ、CO、H2 、CH4 、C2 H6 等のガスが発生する。本発生ガスにより、電池の内圧が上昇する為、特に電槽の機械的強度を強くできない扁平形電池や角形電池に於いて、電池が膨れたり、電池の内部インピーダンスが上昇して、充放電が不能になる等の問題があった。
【0004】
【課題を解決するための手段】
電解液の溶剤又は高分子固体電解質の可塑剤として、耐酸化性及び耐還元性に優れた6員環環状エーテルを用いる。具体的にはテトラヒドロピラン又はテトラヒドロ−γ−ピロンを用いる。
更に、β位の水素がメトキシ基、エトキシ基等のアルコキシル基で置換されたテトラヒドロピラン、テトラヒドロ−γ−ピロンの誘導体を用いると耐酸性が更に向上し、電解液の溶媒の分解に起因するガス発生抑制にとって好ましい。
【0005】
【発明の実施の形態】
一例として、正極がLiCoO2 、負極がリチウムを吸蔵放出可能な炭素から成る非水二次電池に於いて、電解液にLiPF6 を溶解させたテトラヒドロピラン、テトラヒドロ−γ−ピロン又はその誘導体の溶液を用いる。誘導体としては、βの位置の水素をメトキシ基やエトキシ基で置換した2、6ジメトキシ又は2、6ジエトキシジヒドロピラン、2、6ジメトキシ、又は2、6ジエトキシジヒドロ−γ−ピロンを用いる。
【0006】
また、又前記高分子固体電解質の可塑剤に適用する例をあげると、末端にアクリレート等の官能基を有するポリエチレンオキシド(PEO)とポリプロピレンオキシド(PPO)の液状のランダムコポリマーに前記LiPF6 を溶解させたたテトラヒドロピラン、テトラヒドロ−γ−ピロン又はその誘導体の溶液を混合した後、例えば電子線照射してポリマーを架橋し、固体状電解質を得る。
【0007】
【実施例】
以下、本発明の実施例を説明するが、本発明はこれに限定されるものではない。
(本発明1)
平均粒経10μmのLiCoO2 90重量部とケッチェンブラック5重量部の混合物にポリフッ化ビニリデン(以下PVDFと呼ぶ)のN−メチルーピロリドン(以下NMPと呼ぶ)10%溶液50重量部を添加し、混練する。該混練物をアルミ箔集電体上に塗布した後乾燥し、プレスして正極とする。プレス後の塗布層の厚みが100μmとなるように塗布量を調節した。
【0008】
平均粒径15μmのコークス系炭素粒子95重量部にPVDFのNMP10%溶液50重量部を添加し、混練して、銅箔集電体の上に塗布した後乾燥し、プレスして負極とする。プレス後の塗布層の厚みが100μmとなるように塗布量を調節した。
セパレータとしては、3は厚み約25μmポリエチレン製微孔フィルムから成るセパレータを用いた。
電解液には0.5MのLiPF6 −テトラヒドロピラン溶液を用いた。次いで常法により、封口して大きさ50×50mm、厚み約0.5mmのテストセルとした。
【0009】
本セルを充電レート0.5Cで4.2V迄充電し、その後4.2Vの定電圧充電を行った。トータルの充電時間を3時間とした。充電後に於いて電池に膨れは認められなかった。内部インピーダンスは12Ωであった。その後、放電レート0.5C、終止電圧2.7Vの放電で放電容量50mAhと正常な容量を示した。
【0010】
(本発明2)
電解液として、0.5MのLiPF6 −2、6ジメトキシジヒドロピランを用いた以外は電池構成、試験条件等本発明1と同一とした。本発明1と同様充電後に於いて、電池膨れは発生せず、内部インピーダンスは13Ωであった。その後の放電で放電容量47mAhと正常な容量を示した。
【0011】
(本発明3)
電解液として0.5MのLiPF6 −テトラヒドロ−γ−ピロンを用いた以外は電池構成、試験条件等本発明1と同一とした。内部インピーダンス11Ω放電容量49mAhと本発明1及び2と同様良好な試験結果が得られた。
【0012】
(本発明4)
電解液として0.5MのLiPF6 −2、6ジメトキシジヒドロ−γ−ピロンを用いた以外は電池構成、試験条件等本発明1と同一とした。内部インピーダンス15Ω、放電容量が45mAhと本発明1〜3と同様良好な試験結果が得られた。
【0013】
(本発明5)
両端にアクリレート基を有する分子量約10000のPEOとPPOのランダムコポリマー30重量部に0.5MのLiPF6 −2、6ジメトキシジヒドロピラン溶液70重量部を混合して、粘液状とした。
【0014】
平均粒経10μmのLiCoO2 90重量部とケッチェンブラック5重量部の混合粉末70重量部と前記粘液30重量部を混練して、ペースト状とした。本ペーストを厚み約30μmのアルミ箔上に、厚み約100μmでコーティングした。本コーティング部に電子線を照射して、硬化させ、正極とした。
【0015】
平均粒径15μmのコークス系炭素粉末60重量部と前記粘液40重量部を混練してペースト状とした。本ペーストを厚み約20μmの銅箔上に、厚み約100μmでコーティングした。本コーティング部に電子線を照射して、硬化させ、負極とした。
【0016】
前記粘液50重量部にサブミクロンの粒度の微細アルミナ粉末50重量部を混練してペースト状とした。本ペーストを前記正極の表面に厚み約50μmでコーティングした後電子線を照射して、セパレータ層を形成した。このようにして作製した正極、セパレータ、負極を積層した後、本発明1と同様に封口して、テストセルとした。
【0017】
本テストセルを充電レート0.2Cで4.2V迄充電、更に4.2V定電圧で充電した。トータル充電時間を8時間とした。
充電後に於いて、セルに膨れは認められず、内部インピーダンス28Ωで、その後、放電レート0.2C,終止電圧2.7Vで放電したところ、49mAhと正常な容量を示した。
【0018】
(本発明6)
可塑剤として、2、6ジメトキシジヒドロピランに代えて2、6ジメトキシジヒドロ−γ−ピロンを用いた以外は、本発明5と同一の電池構成とし、同一の試験に供した。内部インピーダンス31Ω、放電容量47mAhと本発明5と同様良好な結果が得られた。
【0019】
(比較例1)電解液として0.5MのLiPF6−プロピレンカーボネート/ジエチルカーボネート混合系(以下PC/DECと呼ぶ)を用いた以外は、電池の構成、試験条件等本発明1と同一とした。充電後セルに膨れが認められ、インピーダンスが1000Ω以上に増大してしまい、その後の放電充電が不能となった。
【0020】
(比較例2)
可塑剤として、PC/DECを用いた以外は、電池の構成、試験条件等本発明5と同一とした。
充電後セルに膨れが認められ、インピーダンスが1000Ω以上に増大してしまい、その後の放電充電が不能となった。
【0021】
【発明の効果】
本発明は、負極がリチウムを吸蔵放出可能な炭素や遷移金属の酸化物又はカルコゲン化物から成る非水二次電池に対して、1サイクル目の充電時に電解液の分解に起因する電池の膨れ、内部インピーダンス増大に伴う充放電性能の低下を抑制するもので、電池の安全性、信頼性、安全性向上にとって有効なものであり、その工業的価値の高いものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a non-aqueous secondary battery in which the positive electrode is a transition metal oxide or chalcogenide, a conductive polymer, the negative electrode is carbon or a lithium alloy capable of inserting and extracting lithium, and the electrolyte is an organic electrolyte or a polymer solid electrolyte. Things.
[0002]
[Prior art]
Among nonaqueous secondary batteries in which the positive electrode is made of a transition metal oxide or chalcogenide or a conductive polymer, the positive electrode is particularly based on a lithium electrode (Li / Li + ) such as LiCoO 2 , LiNiO 2 , or LiMn 2 O 4. Batteries operating at 3.5 to 4.3 V have attracted attention because of their high energy density and have been commercialized. These ethylene carbonate Ne chromatography TMG as a solvent of the electrolyte of the battery, propylene carbonate ne over preparative, carbonic esters such as diethyl carbonate Ne over bets are commonly used.
[0003]
[Problems to be solved by the invention]
In the conventional battery, particularly at the time of charging in the first cycle, a chemical decomposition reaction of the carbonate ester constituting the solvent of the electrolytic solution occurs on the surfaces of the positive electrode and the negative electrode, and CO, H 2 , CH 4 , C 2 H 6 Gas is generated. Because the generated gas increases the internal pressure of the battery, the battery swells and the internal impedance of the battery increases, especially in flat batteries and square batteries, where the mechanical strength of the battery case cannot be increased. There were problems such as becoming impossible.
[0004]
[Means for Solving the Problems]
As a solvent for the electrolytic solution or a plasticizer for the solid polymer electrolyte, a 6-membered cyclic ether having excellent oxidation resistance and reduction resistance is used. Specifically, tetrahydropyran or tetrahydro-γ-pyrone is used.
Further, when a derivative of tetrahydropyran or tetrahydro-γ-pyrone in which the hydrogen at the β-position is substituted with an alkoxyl group such as a methoxy group or an ethoxy group is used, the acid resistance is further improved, and the gas resulting from the decomposition of the solvent of the electrolytic solution is used. It is preferable for suppressing generation.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
As an example, in a non-aqueous secondary battery in which the positive electrode is made of LiCoO 2 and the negative electrode is made of carbon capable of inserting and extracting lithium, a solution of tetrahydropyran, tetrahydro-γ-pyrone or a derivative thereof in which LiPF 6 is dissolved in the electrolyte solution Is used. As the derivative, 2,6 dimethoxy or 2,6 diethoxydihydropyran, 2,6 dimethoxy, or 2,6 diethoxydihydro-γ-pyrone in which the hydrogen at position β is substituted with a methoxy group or an ethoxy group is used.
[0006]
In addition, as an example of application to the plasticizer of the polymer solid electrolyte, LiPF 6 is dissolved in a liquid random copolymer of polyethylene oxide (PEO) and polypropylene oxide (PPO) having a functional group such as acrylate at the end. After mixing the thus-prepared solution of tetrahydropyran, tetrahydro-γ-pyrone or a derivative thereof, the polymer is crosslinked by, for example, irradiation with an electron beam to obtain a solid electrolyte.
[0007]
【Example】
Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto.
(Invention 1)
To a mixture of 90 parts by weight of LiCoO 2 having an average particle diameter of 10 μm and 5 parts by weight of Ketjen black, 50 parts by weight of a 10% solution of N-methyl-pyrrolidone (hereinafter referred to as NMP) of polyvinylidene fluoride (hereinafter referred to as PVDF) is added. , Knead. The kneaded material is applied on an aluminum foil current collector, dried, and pressed to obtain a positive electrode. The amount of coating was adjusted so that the thickness of the coating layer after pressing was 100 μm.
[0008]
To 95 parts by weight of coke-based carbon particles having an average particle size of 15 μm, 50 parts by weight of a 10% solution of PVDF in NMP is added, kneaded, applied on a copper foil current collector, dried, and pressed to form a negative electrode. The amount of coating was adjusted so that the thickness of the coating layer after pressing was 100 μm.
As the separator 3, a separator made of a polyethylene microporous film having a thickness of about 25 μm was used.
The electrolyte used was a 0.5 M LiPF 6 -tetrahydropyran solution. Next, the test cell was sealed by a conventional method to obtain a test cell having a size of 50 × 50 mm and a thickness of about 0.5 mm.
[0009]
This cell was charged to 4.2 V at a charge rate of 0.5 C, and then was charged at a constant voltage of 4.2 V. The total charging time was 3 hours. No swelling was observed in the battery after charging. The internal impedance was 12Ω. Thereafter, a discharge capacity of 50 mAh and a normal capacity were exhibited at a discharge rate of 0.5 C and a discharge voltage of 2.7 V.
[0010]
(Invention 2)
Except that 0.5 M LiPF 6 -2,6 dimethoxydihydropyran was used as the electrolytic solution, the battery configuration, test conditions, and the like were the same as those of the first invention. After charging, the battery did not swell and the internal impedance was 13Ω as in the case of Invention 1. The subsequent discharge showed a normal discharge capacity of 47 mAh.
[0011]
(Invention 3)
Except that 0.5 M LiPF 6 -tetrahydro-γ-pyrone was used as the electrolytic solution, the battery configuration, test conditions, and the like were the same as those of the first invention. The internal impedance was 11Ω and the discharge capacity was 49 mAh, which was the same as the results of the present inventions 1 and 2 and good test results.
[0012]
(Invention 4)
Except that 0.5 M LiPF 6 -2,6 dimethoxydihydro-γ-pyrone was used as the electrolytic solution, the battery configuration, test conditions, and the like were the same as those of the first invention. The internal impedance was 15Ω, the discharge capacity was 45 mAh, and good test results were obtained as in the case of the first to third inventions.
[0013]
(Invention 5)
Both ends by mixing LiPF 6 -2,6-dimethoxy-dihydropyran solution 70 parts by weight of 0.5M in 30 parts by weight of a random copolymer having a molecular weight of about 10000 of PEO and PPO having an acrylate group, and a mucus-like.
[0014]
90 parts by weight of LiCoO 2 having an average particle diameter of 10 μm, 70 parts by weight of a mixed powder of 5 parts by weight of Ketjen black, and 30 parts by weight of the mucus were kneaded to form a paste. This paste was coated on an aluminum foil having a thickness of about 30 μm to a thickness of about 100 μm. The coating was irradiated with an electron beam and cured to obtain a positive electrode.
[0015]
60 parts by weight of a coke-based carbon powder having an average particle size of 15 μm and 40 parts by weight of the mucus were kneaded to form a paste. This paste was coated on a copper foil having a thickness of about 20 μm to a thickness of about 100 μm. The coating was irradiated with an electron beam and cured to obtain a negative electrode.
[0016]
50 parts by weight of the above-mentioned mucus and 50 parts by weight of fine alumina powder having a submicron particle size were kneaded to form a paste. This paste was coated on the surface of the positive electrode with a thickness of about 50 μm, and then irradiated with an electron beam to form a separator layer. After laminating the positive electrode, the separator and the negative electrode produced in this way, they were sealed in the same manner as in the present invention 1 to obtain a test cell.
[0017]
This test cell was charged at a charging rate of 0.2 C up to 4.2 V, and further charged at a constant voltage of 4.2 V. The total charging time was 8 hours.
After charging, no swelling was observed in the cell, and the cell was discharged at an internal impedance of 28Ω and a discharge rate of 0.2 C and a cutoff voltage of 2.7 V. As a result, a normal capacity of 49 mAh was shown.
[0018]
(Invention 6)
Except that 2,6 dimethoxydihydro-γ-pyrone was used in place of 2,6 dimethoxydihydropyran as the plasticizer, the battery configuration was the same as that of the fifth invention, and the same test was performed. The internal impedance was 31Ω and the discharge capacity was 47 mAh.
[0019]
(Comparative Example 1) LiPF of 0.5M 6 as an electrolytic solution - except using flop Ropirenkabone over DOO / di et Chirukabone over preparative mixing system (hereinafter referred to as PC / DEC), the configuration of the battery, the test conditions present invention Same as 1. After charging, swelling was observed in the cell, and the impedance was increased to 1000Ω or more, so that subsequent discharging and charging became impossible.
[0020]
(Comparative Example 2)
Except that PC / DEC was used as the plasticizer, the configuration of the battery, the test conditions, and the like were the same as those of the fifth invention.
After charging, swelling was observed in the cell, and the impedance was increased to 1000Ω or more, so that subsequent discharging and charging became impossible.
[0021]
【The invention's effect】
The present invention is directed to a non-aqueous secondary battery in which the negative electrode is made of an oxide or chalcogenide of carbon or a transition metal capable of inserting and extracting lithium, and the battery swells due to decomposition of the electrolytic solution during the first cycle of charging, It suppresses a decrease in charge / discharge performance due to an increase in internal impedance, is effective for improving the safety, reliability, and safety of a battery, and has high industrial value.
Claims (3)
Priority Applications (1)
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JP01376896A JP3567954B2 (en) | 1996-01-30 | 1996-01-30 | Non-aqueous secondary battery |
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JP01376896A JP3567954B2 (en) | 1996-01-30 | 1996-01-30 | Non-aqueous secondary battery |
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JPH09213368A JPH09213368A (en) | 1997-08-15 |
JP3567954B2 true JP3567954B2 (en) | 2004-09-22 |
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EP3273520B1 (en) | 2015-03-16 | 2020-05-06 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte and nonaqueous electrolyte secondary cell in which same is used |
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JP2552652B2 (en) * | 1986-03-25 | 1996-11-13 | 日本電信電話株式会社 | Electrolyte for lithium battery |
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