JPH03245458A - Carbonaceous material, manufacture thereof, and non-aqueous electrolyte battery using thereof - Google Patents
Carbonaceous material, manufacture thereof, and non-aqueous electrolyte battery using thereofInfo
- Publication number
- JPH03245458A JPH03245458A JP2038343A JP3834390A JPH03245458A JP H03245458 A JPH03245458 A JP H03245458A JP 2038343 A JP2038343 A JP 2038343A JP 3834390 A JP3834390 A JP 3834390A JP H03245458 A JPH03245458 A JP H03245458A
- Authority
- JP
- Japan
- Prior art keywords
- boron
- carbonaceous material
- lithium
- amount
- 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.)
- Granted
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 56
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 manufacture thereof Substances 0.000 title description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052796 boron Inorganic materials 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011368 organic material Substances 0.000 claims abstract description 18
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 15
- 238000010000 carbonizing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 10
- 238000003763 carbonization Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052810 boron oxide Inorganic materials 0.000 abstract description 3
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 229920000178 Acrylic resin Polymers 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000005011 phenolic resin Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 15
- 229960002645 boric acid Drugs 0.000 description 15
- 235000010338 boric acid Nutrition 0.000 description 15
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 15
- 239000004327 boric acid Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 241001669573 Galeorhinus galeus Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005618 boron oxoacid group Chemical group 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- MTKRXXSLFWZJTB-UHFFFAOYSA-N oxo(oxoboranyl)borane Chemical compound O=BB=O MTKRXXSLFWZJTB-UHFFFAOYSA-N 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphene Chemical compound C1=CC=C2C=C3C4=CC5=CC=CC=C5C=C4C=CC3=CC2=C1 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、リチウムをドープ・脱トープする炭素質材料
及びその製造方法に関するものであり、さらにはかかる
炭素質材料をｘｉとする非水電解液電池に関するもので
ある。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a carbonaceous material doped with lithium and detopped, and a method for producing the same, and further relates to a non-aqueous electrolysis method using such a carbonaceous material as xi. It is related to liquid batteries.
本発明は、有機材料を炭素化して炭素質材料とする際に
、ホウ素化合物を添加することでリチウムに対するトー
プ量の大きな炭素質材料となし、これを負極に用いて充
放電容量が大きな非水電解液電池を提供しようとするも
のである。In the present invention, when an organic material is carbonized to make a carbonaceous material, a boron compound is added to produce a carbonaceous material with a large amount of tope for lithium, and this is used as a negative electrode to form a non-aqueous material with a large charge/discharge capacity. The present invention aims to provide an electrolyte battery.
〔従来の技術）
電子機器の小型化に伴い、電池の高エネルギー密度化が
要求されており、かかる要求に応えるべく種々の新しい
二次電池の提案がなされている。[Prior Art] As electronic devices become smaller, batteries are required to have higher energy density, and various new secondary batteries have been proposed to meet this demand.
その一つに、リチウムを用いた非水電解液電池があり、
実用化に向けて研究が活発に行われている。One of these is a non-aqueous electrolyte battery that uses lithium.
Research is being actively conducted toward practical application.
しかしながら、かかる非水電解液電池の実用化に際して
は、負極に金属リチウムを用いていることに伴う次のよ
うな欠点が特に問題となっている。However, when putting such non-aqueous electrolyte batteries into practical use, the following drawbacks associated with the use of metallic lithium for the negative electrode pose particular problems.
すなわち、
■充電に５〜ＩＯ時間を必要とし、急速充電性に劣るこ
と、
■サイクル寿命が短いこと、
等である。That is, (1) it requires 5 to IO hours for charging and is inferior in rapid charging performance, (2) its cycle life is short, and so on.
これらはいずれもリチウム自身に起因するもので、充放
電の繰り返しに伴うリチウム負極の形態変化、デンドラ
イト （樹状結晶）の形成、リチウムの不動態化等がそ
の原因とされている。All of these are caused by the lithium itself, and are thought to be caused by changes in the shape of the lithium negative electrode due to repeated charging and discharging, the formation of dendrites, and passivation of lithium.
上記問題を解決する一手法として、負極に金属リチウム
を単体で用いるのではなく、炭素質材料にドープさせて
用いることが提案されている。これは、リチウムの炭素
層間化合物が電気化学的に容易に形成できることを利用
したものであり、例えば炭素質材料を負極として非水電
解液中で充電を行うと、正極中のリチウムは電気化学的
に負極炭素の眉間にドープされる。そして、リチウムを
ドープした炭素質材料は、リチウム電極として作用し、
放電に体ってリチウムは炭素層間から脱トープされ、正
極中に戻る。As one method for solving the above problem, it has been proposed to use metallic lithium as a negative electrode by doping it into a carbonaceous material instead of using it alone. This takes advantage of the fact that carbon intercalation compounds of lithium can be easily formed electrochemically. For example, when a carbonaceous material is used as a negative electrode and charged in a non-aqueous electrolyte, lithium in the positive electrode is electrochemically The negative electrode is doped between the eyebrows of carbon. Then, the lithium-doped carbonaceous material acts as a lithium electrode,
During discharge, lithium is detopped from between the carbon layers and returns to the positive electrode.
〔発明が解決しようとする課Ｈ］
ところで、このときの炭素質材料の単位重量当たりの電
気容量は、リチウムのドープ量によって決まる。したが
って電池の充放電容量を大きくするためには、炭素質材
料のリチウムに対するドープ量を出来る限り理論最大容
量に近づけることが必要である。たとえば、グラファイ
トにおいては炭素原子６個に対してリチウム原子１個が
ドープされた場合に理論最大容量が得られる。[Problem H to be Solved by the Invention] Incidentally, the electric capacity per unit weight of the carbonaceous material at this time is determined by the amount of lithium doped. Therefore, in order to increase the charge/discharge capacity of a battery, it is necessary to bring the amount of doping of lithium in the carbonaceous material as close to the theoretical maximum capacity as possible. For example, in graphite, the theoretical maximum capacity is obtained when six carbon atoms are doped with one lithium atom.
従来、この種の電池の負極に用いられる炭素質材料とし
ては、例えば特開昭６２−１２２０６６号公報、あるい
は特開昭６２−９０８６３号公報などに記載されるよう
に、有機材料を炭素化して得られる炭素質材料が知られ
ている。Conventionally, carbonaceous materials used for the negative electrode of this type of battery include carbonized organic materials, as described in, for example, JP-A-62-122066 or JP-A-62-90863. The resulting carbonaceous materials are known.
しかしながら、これまでの炭素質材料では、リチウムの
ドープ量が不十分で、理論値の半分程度の容量しか得ら
れないのが実情である。However, the actual situation is that in conventional carbonaceous materials, the amount of lithium doped is insufficient and the capacity is only about half of the theoretical value.
そこで本発明は、前述の従来の実情に鑑みて提案される
ものであって、リチウムのドープ量の大きな炭素質材料
およびその製造方法を開発することを目的とし、これに
より充放電容量が大きく、サイクル寿命特性に優れた非
水電解液電池を掃供することを目的とする。Therefore, the present invention is proposed in view of the above-mentioned conventional situation, and aims to develop a carbonaceous material doped with a large amount of lithium and a method for producing the same, thereby achieving a large charge/discharge capacity. The purpose is to provide non-aqueous electrolyte batteries with excellent cycle life characteristics.
本発明者等は、前述の目的を達成せんものと鋭意検討を
重ねた結果、炭素化に際してホウ素化合物を添加するこ
とが得られる炭素質材料のリチウムに対するドープ量を
大きくする上で非常に有効であることを見出した。本発
明はかかる知見にもとづいて完成されたものである。As a result of intensive studies to achieve the above-mentioned objective, the present inventors have found that adding a boron compound during carbonization is extremely effective in increasing the amount of lithium doped in the resulting carbonaceous material. I discovered something. The present invention was completed based on this knowledge.
すなわち、本発明の炭素質材料は、有機材料が炭素化さ
れてなり、ホウ素を０．１〜２．０重量％含有すること
を特徴とするものである。That is, the carbonaceous material of the present invention is made by carbonizing an organic material and is characterized by containing 0.1 to 2.0% by weight of boron.
また、本発明の炭素質材料の製造方法は、有機材料もし
くは炭素質材料に対し、ホウ素換夏で０．１５〜２．５
重量％のホウ素化合物を添加し、炭素化することを特徴
とするものである。In addition, in the method for producing a carbonaceous material of the present invention, boron exchange rate is 0.15 to 2.5% for an organic material or a carbonaceous material.
It is characterized by adding % by weight of a boron compound and carbonizing it.
さらに、本発明の非水電解液電池は、有機材料が炭素化
されホウ素を０．１〜２．０重量％含有してなる炭素質
材料を負極とし、リチウムを含んだ正極と非水電解液と
を有してなることを特徴とするものである。Furthermore, the nonaqueous electrolyte battery of the present invention uses a carbonaceous material obtained by carbonizing an organic material and containing 0.1 to 2.0% by weight of boron as a negative electrode, a positive electrode containing lithium, and a nonaqueous electrolyte. It is characterized by having the following.
本発明の炭素質材料は、有機材料を焼成等の手法により
炭素化して得られるものである６出発原料となる有機材
料としては、フェノール樹脂、アクリル樹脂、ハロゲン
化ビニル樹脂、ポリアミドイミド樹脂、ポリアミド樹脂
、ポリアセチレン、ポリ（ｐ−フェニレン）等の共役系
樹脂、セルロース樹脂等、任意の有機高分子系化合物を
使用することができる。The carbonaceous material of the present invention is obtained by carbonizing an organic material by a method such as sintering.6 Organic materials serving as starting materials include phenol resin, acrylic resin, vinyl halide resin, polyamideimide resin, polyamide resin, etc. Any organic polymeric compound such as a resin, a conjugated resin such as polyacetylene or poly(p-phenylene), or a cellulose resin can be used.
さらには、フルフリルアルコールあるいはフルフラール
のホモポリマー、コポリマーよりなるフラン樹脂も好適
である。具体的には、フルフリルアルコール、フルフリ
ルアルコール＋ジメチロール尿素、フルフリルアルコー
ル＋ホルムアルデヒド、フルフラール＋フェノール、フ
ルフラール＋ケトン類等よりなる重合体が挙げられる。Furthermore, furan resins made of furfuryl alcohol or furfural homopolymers or copolymers are also suitable. Specifically, polymers consisting of furfuryl alcohol, furfuryl alcohol + dimethylol urea, furfuryl alcohol + formaldehyde, furfural + phenol, furfural + ketones, etc. can be mentioned.
このフラン樹脂を炭素化した炭素質材料は、（００２）
面の面間隔ｄ０゜２が３．７０Å以上であり、示差熱分
析（ＤＴＡ）において７００°Ｃ以上に発熱ピークを持
たず、電池の負極材として非常に良好な特性を示す。The carbonaceous material obtained by carbonizing this furan resin is (002)
The interplanar spacing d0°2 is 3.70 Å or more, there is no exothermic peak above 700°C in differential thermal analysis (DTA), and it exhibits very good characteristics as a negative electrode material for batteries.
その他、ナフタレン、フェナントレン、アントラセン、
トリフェニレン、ピレン、クリセン ナフタセン、ビセ
ン、ペリレン、ペンタフェン ペンタセン等の縮合多環
炭化水素化合物、その誘導体（例えば前記各化合物のカ
ルボン酸、カルボン酸無水物、カルボン酸イミド等）、
前記各化合物の混合物を主成分とする各種ピッチ、イン
ドールイソインドール、キノホウ素、イソキノホウ素。Others include naphthalene, phenanthrene, anthracene,
Condensed polycyclic hydrocarbon compounds such as triphenylene, pyrene, chrysene, naphthacene, bicene, perylene, pentaphene, and pentacene, derivatives thereof (for example, carboxylic acids, carboxylic acid anhydrides, carboxylic acid imides, etc. of each of the above compounds),
Various pitches, indoleisoindole, quinoboron, and isoquinoboron containing mixtures of the above-mentioned compounds as main components.
キノキサホウ素、フタラジン、カルバゾール、アクリジ
ン、フェナジン、フェナントレン等の縮合複素環化合物
、その誘導体等も使用可能である。Fused heterocyclic compounds such as quinoxaboron, phthalazine, carbazole, acridine, phenazine, and phenanthrene, and derivatives thereof can also be used.
これら有機材料を焼成する等の手法により熱処理して炭
素化する。炭素化温度は出発原料によっても異なるが、
通常は５００〜３０００℃とされる。These organic materials are heat-treated by a method such as firing to carbonize them. The carbonization temperature varies depending on the starting material, but
The temperature is usually 500 to 3000°C.
本発明においては、この炭素化の際にホウ素化合物を添
加することで、得られる炭素質材料のリチウムに対する
ドープ量を大きなものとする。In the present invention, by adding a boron compound during carbonization, the amount of lithium doped in the resulting carbonaceous material is increased.
ホウ素化合物としては、二酸化ニホウ素、三酸化ニホウ
素（いわゆる酸化ホウ素）、 三酸化四ホウ素、五酸化
四ホウ素等のホウ素の酸化物や、オルトホウ酸（いわゆ
るホウ酸）、メタホウ酸、四ホウ酸１次ホウ酸等のホウ
素のオキソ酸およびその塩等が挙げられる。これらのホ
ウ素化合物は、いずれも水？８液の状態で炭素化のため
の反応系に添加することができる。Examples of boron compounds include boron oxides such as diboron dioxide, diboron trioxide (so-called boron oxide), tetraboron trioxide, and tetraboron pentoxide, orthoboric acid (so-called boric acid), metaboric acid, and tetraboric acid. Examples include boron oxoacids such as primary boric acid and salts thereof. Are all these boron compounds water? It can be added to the reaction system for carbonization in the form of 8 liquids.
本発明では、有機材料の炭素化の際に添加されるホウ素
化合物の添加量はこれら有機材料もしくは炭素質材料に
対してホウ素換算で０．１５〜２．５重量％、また炭素
質材料中のホウ素の含量は０．１〜２．０重量％とする
。これらの範囲は、本発明者らが行った次のような予備
実験にもとづいて決定されたものである。In the present invention, the amount of the boron compound added during carbonization of organic materials is 0.15 to 2.5% by weight in terms of boron relative to these organic materials or carbonaceous materials, and The boron content is 0.1 to 2.0% by weight. These ranges were determined based on the following preliminary experiments conducted by the present inventors.
まず第１図に、ポリフルフリルアルコール樹脂（無水マ
レイン酸触媒）焼成体の焼成に際しでホウ酸を添加した
場合のホウ素仕込み置と焼成体中に残存するホう素の量
との関係を示す。ホウ素の残存量は、誘導結合型プラズ
マ発光分光分析により定量した。また、ホウ素の仕込み
量は、ホウ酸の添加量から換算したものである。これよ
り、ホウ素残存量はホウ素仕込み量にほぼ比例して増大
していることがわかる。First, FIG. 1 shows the relationship between the boron charging device and the amount of boron remaining in the fired product when boric acid is added during firing of the polyfurfuryl alcohol resin (maleic anhydride catalyst) fired product. The remaining amount of boron was determined by inductively coupled plasma emission spectrometry. Further, the amount of boron charged is calculated from the amount of boric acid added. From this, it can be seen that the residual amount of boron increases almost in proportion to the amount of boron charged.
第２図には、かかる焼成体を負極とした電池における連
続充放電可能電気量のホウ素仕込み量による変化を示す
。これより、焼成に際してのホウ素の添加は充放電容量
を増大させる上で有効であるが、その変化のパターンに
は極大値が存在することがわかる。つまり、負極に残存
するホウ素量は多いほど好ましいとは一概に言えないの
である。FIG. 2 shows the change in the amount of electricity that can be continuously charged and discharged in a battery using such a fired body as a negative electrode, depending on the amount of boron charged. This shows that although the addition of boron during firing is effective in increasing the charge/discharge capacity, there is a maximum value in the pattern of its change. In other words, it cannot be said unequivocally that the larger the amount of boron remaining in the negative electrode, the better.
一般に、炭素質材料中の炭素原子がホウ素原子に置換さ
れると電気伝導度が低下すると考えられている。そこで
、ホウ素仕込み量と電池の内部抵抗との関係を調べたと
ころ、第３図に示すように、内部抵抗はホウ素仕込み量
の増大にともなって増大していた。It is generally believed that when carbon atoms in a carbonaceous material are replaced with boron atoms, electrical conductivity decreases. Therefore, when the relationship between the amount of boron charged and the internal resistance of the battery was investigated, as shown in FIG. 3, the internal resistance increased as the amount of boron charged increased.
したがって、ホウ素の仕込み量および残存量は電池の実
用性能を考慮して最適範囲に規定される必要があり、上
述の範囲が決定された。ホウ素化合物の添加量が前記範
囲よりも少なく、その結果として炭素質材料中のホウ素
の割合が少なくなりすぎると、リチウムのドープ量を効
果的に増大させることができない。逆に、ホウ素化合物
の添加量が前記の範囲よりも多く、その結果として炭素
質材料中のホウ素の割合が多くなりすぎると、内部抵抗
が増大する他、リチウムのドープに実質的に関与する炭
素質材料の割合を減少させる虞れがある。Therefore, the amount of boron charged and the remaining amount must be determined within the optimum range in consideration of the practical performance of the battery, and the above-mentioned range was determined. If the amount of the boron compound added is less than the above range, and as a result, the proportion of boron in the carbonaceous material becomes too small, the amount of lithium doped cannot be effectively increased. On the other hand, if the amount of boron compound added is larger than the above range, and as a result, the proportion of boron in the carbonaceous material becomes too large, the internal resistance will increase and the carbon material that is substantially involved in lithium doping will increase. There is a risk of reducing the proportion of quality materials.
前述の炭素質材料を非水電解液電池の負極とする場合、
正極材料としては十分な量のリチウムを含んだ材料を使
用することが好ましく、一般式ＬｉＭＯ□ （ただし、
ＭはＣｏ、Ｎｉの少な（とも１種を表す。）で表される
複合金属酸化物やリチウムを含んだ眉間化合物等が使用
される。特にＬｉＣｏ０．やＬ ｉ Ｃｏｏ、ｓＮ ｉ
ｏ、ｚｏｚ等を使用した場合に良好な特性が発揮され
る。When using the aforementioned carbonaceous material as the negative electrode of a non-aqueous electrolyte battery,
It is preferable to use a material containing a sufficient amount of lithium as the positive electrode material, and the general formula LiMO□ (however,
For M, a composite metal oxide containing a small amount of Co or Ni (both represent one type), a lithium-containing compound, or the like is used. Especially LiCo0. YaL i Coo, sN i
Good characteristics are exhibited when o, zoz, etc. are used.
非水電解液は、有機溶媒と電解質を適宜組み合わせて調
製されるが、これらを機溶媒や電解質としてはこの種の
電池に用いられるものであればいずれも使用可能である
。The non-aqueous electrolyte is prepared by appropriately combining an organic solvent and an electrolyte, but any organic solvent or electrolyte that is used in this type of battery can be used.
例示するならば、有機溶媒としてはプロピレンカーボネ
ート、エチレンカーボネート、１２ジメトキシエタン、
１．２−シェドキンエタン、γ−ブチロラクトン、テト
ラヒドロフラン、２メチルテトラヒドロフラン、１．３
−ジオキソラン、４−メチル−１３−ジオキソラン、ジ
エチルエーテル、スルホラン、メチルスルホラン、アセ
トニトリル、プロピオニトリル、アニソール等である。To illustrate, examples of organic solvents include propylene carbonate, ethylene carbonate, 12 dimethoxyethane,
1.2-shedquin ethane, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1.3
-dioxolane, 4-methyl-13-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propionitrile, anisole and the like.
電解質としては、ＬｉＣｆ０．、ＬｉＡｓＦ、、１ｉＰ
Ｆａ、ＬｉＢＦ４、Ｌ ｉ Ｂ（Ｃ６Ｈ５）４、ＣＨ３
Ｓ Ｏｓ Ｌ ｉ 、、ＣＦ ３ Ｓ Ｏ３Ｌ ｉ、Ｌ
ｉＣ１、ＬｉＢｒ等が挙げられる。As an electrolyte, LiCf0. ,LiAsF,,1iP
Fa, LiBF4, LiB(C6H5)4, CH3
S Os L i ,, CF 3 S O3 L i,L
Examples include iC1, LiBr, and the like.
有機材料を炭素化して炭素質材料とする際に、ホウ酸等
のホウ素化合物を添加しておくと、リチウムのトープ量
が大きなものとなり、脱ドープ量／ドー装置で表される
充放電効率も大きなものとなる。If a boron compound such as boric acid is added when carbonizing an organic material to make a carbonaceous material, the amount of lithium tope increases, and the charge/discharge efficiency expressed as dedoping amount/doping device also increases. It becomes something big.
このリチウムのドープ量が大きな炭素質材料を非水電解
質電池の負極とすると、充放電容量が拡大され、充放電
操作の繰り返しによる劣化も抑えられる。When this carbonaceous material doped with a large amount of lithium is used as the negative electrode of a non-aqueous electrolyte battery, the charge/discharge capacity is expanded and deterioration due to repeated charge/discharge operations is suppressed.
以下、本発明を具体的な実験結果にもとづいて説明する
。The present invention will be explained below based on specific experimental results.
実施例１
フルフリルアルコール５００ ｇ、無水マレイン酸１ｇ
、純水２００ｇを混合し、湯浴上で２時間還流させて赤
黒色の粘稠なポリマーを得た。Example 1 Furfuryl alcohol 500 g, maleic anhydride 1 g
, 200 g of pure water were mixed and refluxed on a hot water bath for 2 hours to obtain a reddish-black viscous polymer.
未反応アルコールおよび残留水を真空蒸溜により除去し
た後、得られたポリマー１００ｇに対してホウ酸５ｇ（
ホウ素換算で０．８７ ｇ ）を純水５０ｇに溶解した
水溶液を加えた。After removing unreacted alcohol and residual water by vacuum distillation, 5 g of boric acid (
An aqueous solution of 0.87 g (calculated as boron) dissolved in 50 g of pure water was added.
この混合物を窒素気流中で５００°Ｃ，５時間保持して
炭化した後、１２００°Ｃに昇温し１時間熱処理した。This mixture was carbonized by holding it at 500°C in a nitrogen stream for 5 hours, and then heated to 1200°C and heat-treated for 1 hour.
このようにして得られた炭素質材料の特性は、（００２
）面間距離３．７５人、真密度１．５５ｇ／ｃｍ”ＤＴ
Ａにおける発熱ピーク５９５°Ｃ，ホウ素含量０．４５
重量％であった。The characteristics of the carbonaceous material obtained in this way are (002
) Distance between surfaces 3.75 people, true density 1.55 g/cm”DT
Exothermic peak in A 595°C, boron content 0.45
% by weight.
次に、上記炭素質材料を用いてコイン型の非水電界液電
池を構成した。Next, a coin-shaped non-aqueous electrolyte battery was constructed using the carbonaceous material.
先ず、上記炭素質材料を乳鉢にて粉砕した後、篩により
分級し、３９０メツシユ以下のものを採取した。First, the carbonaceous material was ground in a mortar, then classified using a sieve, and those having a size of 390 mesh or less were collected.
分級した炭素質材料１ｇに結合剤としてポリフッ化ビニ
リデン１００ｍｇを加え、ジメチルホルムアミドを用い
てペースト状とし、これをステンレス製の綱に塗布して
５ｔ／ｃｄの圧力で圧着した。100 mg of polyvinylidene fluoride was added as a binder to 1 g of the classified carbonaceous material, and dimethylformamide was used to form a paste, which was applied to a stainless steel rope and compressed with a pressure of 5 t/cd.
これを適当な形に打ち抜き、負極とした。This was punched out into a suitable shape and used as a negative electrode.
正極は、活物質としてＬｉＮ１ｏ、ｚＣｏ。６，０□を
用い、次のようにして作成した。The positive electrode uses LiN1o and zCo as active materials. It was created as follows using 6.0 □.
ＬｉＮ１ｏ、ｚｃ Ｏｏ、ｍｏｔ ９．１ ｇにグラフ
ァイト６００ｍｇ、ポリ四フッ化エチレン３００ｍｇを
加えて混合した後、そのＩｇを取って成形型に入れ、２
ｔ／ｃｄの圧力でコンプレッション成形し、円盤状の正
極とした。After adding and mixing 600 mg of graphite and 300 mg of polytetrafluoroethylene to 9.1 g of LiN1o, zc Oo, mot, the Ig was taken and put into a mold, and 2
Compression molding was performed at a pressure of t/cd to form a disk-shaped positive electrode.
以上の正極と負極を用い、電解液としてプロピレンカー
ボネートと１，２−ジメトキシエタンの１＝１（体積比
）混合溶媒にＬｉＣｊ２０．を１モル／ｌの割合で溶解
した溶液を用い、さらにセパレータとしてポリプロピレ
ン不織布を用いてコイン型の電池を作成した。このとき
、両極における活物質の使用量は、電気化学当量で比較
した場合に正極が負極に対して十分に大きくなるように
設定し、したがって電池容量が負極規制となるようにし
た。Using the above positive electrode and negative electrode, LiCj20. A coin-shaped battery was prepared by using a solution in which 1 mol/l of 1 mol/l was dissolved and a polypropylene nonwoven fabric as a separator. At this time, the amount of active material used in both electrodes was set so that the positive electrode was sufficiently larger than the negative electrode when compared in terms of electrochemical equivalent, so that the battery capacity was regulated by the negative electrode.
この電池について充放電サイクル試験を行った。A charge/discharge cycle test was conducted on this battery.
充電および放電は共に０．５３ ｍＡ／ ｃ ｍ”の定
電流で行い、放電終止電圧は１．５Ｖとした。ここで、
充電量を３８０ｍＡＨ／ｇ （ただし、炭素質材料Ｉｇ
当たりの充電量。以下間し。）として充放電サイクル試
験を行った結果を第４図に示す。図中、縦軸は放電容Ｎ
（ｍＡＨ／ｇ）、横軸はサイクル回数（回）を表し、本
実施例の結果は曲線Ｉで表す。この結果からも明らかな
ように、本実施例にかかる電池は９０サイクルを経た後
でも安定して高い放電容量を維持しており、グラファイ
トを負極とした場合の理論最大容量（３７２ｍＡＨ／
ｇ）と同等以上の充電量にて充放電が可能であることが
わかる。Both charging and discharging were performed at a constant current of 0.53 mA/cm'', and the discharge end voltage was 1.5V.Here,
Charge amount is 380mAH/g (However, carbonaceous material Ig
Charge amount per unit. For the following time. ) The results of a charge/discharge cycle test are shown in FIG. In the figure, the vertical axis is the discharge capacity N
(mAH/g), the horizontal axis represents the number of cycles (times), and the results of this example are represented by curve I. As is clear from this result, the battery according to this example maintains a stable high discharge capacity even after 90 cycles, and the theoretical maximum capacity (372 mAH/
It can be seen that charging and discharging is possible with a charge amount equal to or higher than g).
また、第５図には充電量を３８０ｍ Ａ Ｈ／ ｇとし
た場合の放電曲線を示す。図中、縦軸は放電電圧（■）
、横軸は放電容量（ｍＡＨ／ｇ）を表し、本実施例の結
果は実線で表す。この際の充放電効率は９８．３％と極
めて良好であった。Further, FIG. 5 shows a discharge curve when the charging amount is 380mAH/g. In the figure, the vertical axis is the discharge voltage (■)
, the horizontal axis represents discharge capacity (mAH/g), and the results of this example are represented by a solid line. The charging/discharging efficiency at this time was extremely good at 98.3%.
比較例１
実施例１と同様にしてポリマーを得た後、ホウ酸水溶液
を加えずに熱処理を施し、炭素質材料を得た。Comparative Example 1 After obtaining a polymer in the same manner as in Example 1, heat treatment was performed without adding an aqueous boric acid solution to obtain a carbonaceous material.
この炭素質材料を用いて実施例１と同様の電池を作成し
、同様の条件で充放電サイクル試験を行った。ただし、
充電量は３２０．３５０．３８０ ｍ Ａ Ｈ／ごと変
化させた。結果を前述の第４図に併せて示す。図中、曲
線■は充Ｅｉｌを３２０ｍ Ａ Ｈ／ ｇとした場合、
曲線■は３５０ｍ Ａ Ｈ／ ｇ、曲線■は１３８０ｍ
Ａ Ｈ／ ｇとした場合にそれぞれ対応する。この結
果、安定した充放電特性が得られるのは充電量がせいぜ
い３２０ｍＡＨ／ｇと低い場合に限られることがわかっ
た。A battery similar to that in Example 1 was prepared using this carbonaceous material, and a charge/discharge cycle test was conducted under the same conditions. however,
The charging amount was varied by 320.350.380 m AH/. The results are also shown in FIG. 4 mentioned above. In the figure, the curve ■ is when the charge Eil is 320mA H/g.
Curve ■ is 350m A H/g, curve ■ is 1380m
This corresponds to the case of A H/g. As a result, it was found that stable charge/discharge characteristics could be obtained only when the charge amount was as low as 320 mAH/g at most.
また、前述の第５図に充電量を３２０ｍ Ａ Ｈ／ ｇ
とした場合の放電曲線を破線で示す。この際の充放電効
率は９７．０％であった。Also, the charging amount shown in Figure 5 above is 320m A H/g.
The discharge curve in this case is shown by a broken line. The charging/discharging efficiency at this time was 97.0%.
実施例２
ポリーＰ−フェニレンテレフタルアミド繊維１０ｇを、
ホウ酸５００ｍｇ（ホウ素換算で８７．５ｍｇ）を純水
１５ｇに溶解した溶液中で湿潤させたた後、窒素気流中
、５００°Ｃで５時間保持して炭化させ、さらに１２０
０°Ｃまで昇温しで１時間の熱処理を行った。このよう
にして得られた炭素質材料の特性は、真密度１．３５ｇ
／ｃｍ″、 ＤＴＡにおける発熱ビーク６ｊＯ’Ｃ，
ホウ素含１０．４５重世％であった。Example 2 10 g of poly P-phenylene terephthalamide fiber,
After moistening 500 mg of boric acid (87.5 mg in terms of boron) in a solution of 15 g of pure water, it was held at 500°C in a nitrogen stream for 5 hours to carbonize, and then
The temperature was raised to 0°C and heat treatment was performed for 1 hour. The characteristics of the carbonaceous material obtained in this way are that the true density is 1.35 g.
/cm'', exothermic peak 6jO'C at DTA,
The boron content was 10.45%.
上記炭素質材料を用いて、実施例１と同様の電池を作成
した。A battery similar to that in Example 1 was created using the above carbonaceous material.
様々な充放電量で充放電サイクル試験を行った結果、３
８０ｍ Ａ Ｈ／ ｇという高い充電量においても安定
した充放電を行えることが判明した。As a result of charge/discharge cycle tests with various charge/discharge amounts, 3
It was found that stable charging and discharging could be performed even at a high charge amount of 80mAH/g.
充電量を３８０ｍＡＨ／ｇとした場合の放電曲線を第６
図に実線で示す。このときの充放電効率は９８．５％で
あった
比較例２
ポリ−ｐ−フェニレンテレフタルアミド繊維にホウ酸を
加えないこと以外は実施例２と全く同様にして電池を作
成し、様々な充電量で充放電サイクル試験を行った。The discharge curve when the charge amount is 380mAH/g is shown in the sixth
Shown in the figure as a solid line. The charging/discharging efficiency at this time was 98.5%. Comparative Example 2 A battery was prepared in the same manner as in Example 2 except that boric acid was not added to the poly-p-phenylene terephthalamide fiber, and various charging A charge/discharge cycle test was conducted on the battery.
その結果、安定した充放電が行われるのは充電量が３６
０ｍ Ａ Ｈ／ ｇ程度までの場合に限らることかわか
った。As a result, stable charging and discharging is possible only when the amount of charge is 36.
It was found that this is limited to cases up to about 0 mAH/g.
充電量を３６０ｍ Ａ Ｈ／ ｇとした場合の放電曲線
を前述の第６図に破線で示す。このときの充放電効率は
９８．０％であった。The discharge curve when the charging amount is 360mAH/g is shown by the broken line in the above-mentioned FIG. 6. The charge/discharge efficiency at this time was 98.0%.
以十の実施例および比較例から明らかなように、有機材
料の炭化および熱処理を行う際にホウ素を共存させるこ
とで、従来より充放電容量の向上した炭素質材料が得ら
れる。特に、各実施例において示されるように、出発原
料を適切に選択すればグラファイトを負極とする場合の
理論最大容量を上回る充放電容量を有する炭素質材料を
も得ることができる。As is clear from the following ten examples and comparative examples, by allowing boron to coexist during carbonization and heat treatment of an organic material, a carbonaceous material with improved charge/discharge capacity than before can be obtained. In particular, as shown in each example, if the starting materials are appropriately selected, it is possible to obtain a carbonaceous material having a charge/discharge capacity that exceeds the theoretical maximum capacity when graphite is used as the negative electrode.
以上、本発明を適用した具体的な実施例について説明し
たが、本発明がこれら実施例に限定されるものではなく
、本発明の要旨を逸脱しない範囲で種々の変更が可能で
ある。Although specific embodiments to which the present invention is applied have been described above, the present invention is not limited to these embodiments, and various changes can be made without departing from the gist of the present invention.
（発明の効果］
以上の説明からも明らかなように、本発明の炭素質材料
はホウ素を含有することから、リチウムに対するドープ
量が大きな炭素質材料を提供することができる。(Effects of the Invention) As is clear from the above description, since the carbonaceous material of the present invention contains boron, it is possible to provide a carbonaceous material with a large amount of lithium doped.
また、本発明の製造方法によれば、簡単な操作で特性の
優れた炭素質材料を製造することができ、特にリチウム
のドープ量や充放電効率（脱ドープ量／ドープＩ）の大
きい炭素質材料を製造することが可能である。Further, according to the production method of the present invention, a carbonaceous material with excellent properties can be produced with simple operations, and in particular, a carbonaceous material with a high lithium doping amount and charge/discharge efficiency (undoping amount/doping I) can be produced. It is possible to manufacture the material.
さらに本発明の非水電解液電池においては、リチウムの
ドープ量や充放電効率の大きな炭素質材料を負極として
いるので、グラファイトを負極とする場合の理論最大容
量をも上回る充放電容量を実現することができ、しかも
サイクル特性や充放電効率に優れた電池を提供すること
が可能である。Furthermore, in the non-aqueous electrolyte battery of the present invention, since the negative electrode is made of a carbonaceous material with a large amount of lithium doped and a high charge/discharge efficiency, it achieves a charge/discharge capacity that exceeds the theoretical maximum capacity when graphite is used as the negative electrode. Furthermore, it is possible to provide a battery with excellent cycle characteristics and charge/discharge efficiency.
第１図はポリフルフリルアルコール樹脂の焼成時におけ
るホウ素仕込み量と得られる焼成体中におけるホウ素残
存量との関係を示す特性図である。
第２図はポリフルフリルアルコール樹脂の焼成における
ホウ素仕込み量と得られる焼成体を負極とする電池の連
続充放電可能電気量との関係を示す特性図である。第３
図はホウ素仕込み量と得られる焼成体を負極とする電池
の内部抵抗との関係を示す特性図である。第４図はポリ
フルフリルアルコール樹脂にホウ酸を添加して作成した
炭素質材料を負極とした非水電解液二次電池の充放電サ
イクル特性をホウ酸を添加しないで作成した炭素質材料
を負極とした電池のそれと比べて示す特性図である。第
５図はポリフルフリルアルコール樹脂にホウ酸を添加し
て作成した炭素質材料を負極とした非水電解液二次電池
の放電曲線をホウ酸を添加しないで作成した炭素質材料
を負極とした電池のそれと比べて示す特性図である。第
６図はポリｐ−フェニレンテレフタルアミド繊維にホウ
酸を添加して作成した炭素質材料を負極とした非水電解
液二次電池の放電曲線をホウ素酸を添加しないで作成し
た炭素質材料を負極とした電池のそれと比べて示す特性
図である。FIG. 1 is a characteristic diagram showing the relationship between the amount of boron charged during firing of polyfurfuryl alcohol resin and the amount of boron remaining in the resulting fired product. FIG. 2 is a characteristic diagram showing the relationship between the amount of boron charged in the firing of polyfurfuryl alcohol resin and the amount of electricity that can be continuously charged and discharged of a battery using the obtained fired body as a negative electrode. Third
The figure is a characteristic diagram showing the relationship between the amount of boron charged and the internal resistance of a battery using the obtained fired body as the negative electrode. Figure 4 shows the charge/discharge cycle characteristics of a nonaqueous electrolyte secondary battery using a carbonaceous material made by adding boric acid to polyfurfuryl alcohol resin as the negative electrode. It is a characteristic diagram shown in comparison with that of a battery of Figure 5 shows the discharge curve of a non-aqueous electrolyte secondary battery using a carbonaceous material made by adding boric acid to polyfurfuryl alcohol resin as the negative electrode, and a carbonaceous material made without boric acid being used as the negative electrode. It is a characteristic diagram shown in comparison with that of a battery. Figure 6 shows the discharge curve of a non-aqueous electrolyte secondary battery using a carbonaceous material made by adding boric acid to poly p-phenylene terephthalamide fiber as the negative electrode, and the discharge curve of a nonaqueous electrolyte secondary battery using a carbonaceous material made without boric acid as the negative electrode. It is a characteristic diagram shown in comparison with that of a battery using a negative electrode.
Claims (3)
２．０重量％含有することを特徴とする炭素質材料。(1) The organic material is carbonized and contains 0.1 to 0.1% boron.
A carbonaceous material characterized by containing 2.0% by weight.
で０．１５〜２．５重量％のホウ素化合物を添加し、炭
素化することを特徴とする炭素質材料の製造方法。(2) A method for producing a carbonaceous material, which comprises adding 0.15 to 2.5% by weight of a boron compound in terms of boron to an organic material or a carbonaceous material and carbonizing it.
量％含有してなる炭素質材料を負極とし、リチウムを含
んだ正極と非水電解液とを有してなる非水電解液電池。(3) Non-aqueous electrolysis comprising a carbonaceous material made of carbonized organic material containing 0.1 to 2.0% by weight of boron as a negative electrode, a positive electrode containing lithium, and a non-aqueous electrolyte. liquid battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2038343A JP3060471B2 (en) | 1990-02-21 | 1990-02-21 | Negative electrode for battery, method for producing the same, and nonaqueous electrolyte battery using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2038343A JP3060471B2 (en) | 1990-02-21 | 1990-02-21 | Negative electrode for battery, method for producing the same, and nonaqueous electrolyte battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03245458A true JPH03245458A (en) | 1991-11-01 |
| JP3060471B2 JP3060471B2 (en) | 2000-07-10 |
Family
ID=12522641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2038343A Expired - Fee Related JP3060471B2 (en) | 1990-02-21 | 1990-02-21 | Negative electrode for battery, method for producing the same, and nonaqueous electrolyte battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3060471B2 (en) |
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|---|---|---|---|---|
| JPH05182668A (en) * | 1991-12-27 | 1993-07-23 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| EP0692833A1 (en) | 1994-07-08 | 1996-01-17 | Moli Energy (1990) Limited | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| US5536597A (en) * | 1993-12-17 | 1996-07-16 | Mitsubishi Gas Chemical Company | Lithium secondary battery employing a non-aqueous electrolyte |
| US5580538A (en) * | 1992-03-18 | 1996-12-03 | Matsushita Electric Industrial Co., Ltd. | Process for producing a negative electrode for a storage battery with a non-aqueous electrolyte |
| EP0762522A1 (en) * | 1995-08-18 | 1997-03-12 | PETOCA, Ltd | Boron containing carbon material for lithium secondary battery and process for producing the same |
| US5624606A (en) * | 1994-05-03 | 1997-04-29 | Moli Energy (1990) Limited | Carbonaceous host compounds and use as anodes in rechargeable batteries |
| US5679480A (en) * | 1993-07-26 | 1997-10-21 | Mitsubishi Gas Chemical Company, Inc. | Lithium secondary battery employing a non-aqueous media |
| US5698340A (en) * | 1995-03-03 | 1997-12-16 | Moli Energy (1990) Limited | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| WO1998024134A1 (en) * | 1996-11-26 | 1998-06-04 | Kao Corporation | Negative electrode material for nonaqueous secondary battery |
| JPH10233208A (en) * | 1996-12-20 | 1998-09-02 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| EP1117141A1 (en) * | 1999-07-21 | 2001-07-18 | Mitsubishi Materials Corporation | Carbon powder having enhanced electrical characteristics and use of the same |
| US6355377B1 (en) | 2000-03-07 | 2002-03-12 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and method of preparing same |
| WO2002093666A1 (en) * | 2001-05-15 | 2002-11-21 | Fdk Corporation | Nonaqueous electrolytic secondary battery and method of producing anode material thereof |
| US6489026B1 (en) | 1999-03-25 | 2002-12-03 | Showa Denko K.K. | Carbon fiber, method for producing the same and electrode for cell |
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1990
- 1990-02-21 JP JP2038343A patent/JP3060471B2/en not_active Expired - Fee Related
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05182668A (en) * | 1991-12-27 | 1993-07-23 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US5580538A (en) * | 1992-03-18 | 1996-12-03 | Matsushita Electric Industrial Co., Ltd. | Process for producing a negative electrode for a storage battery with a non-aqueous electrolyte |
| US5679480A (en) * | 1993-07-26 | 1997-10-21 | Mitsubishi Gas Chemical Company, Inc. | Lithium secondary battery employing a non-aqueous media |
| US5536597A (en) * | 1993-12-17 | 1996-07-16 | Mitsubishi Gas Chemical Company | Lithium secondary battery employing a non-aqueous electrolyte |
| US5624606A (en) * | 1994-05-03 | 1997-04-29 | Moli Energy (1990) Limited | Carbonaceous host compounds and use as anodes in rechargeable batteries |
| US5587256A (en) * | 1994-07-08 | 1996-12-24 | Moli Energy (1990) Limited | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| EP0692833A1 (en) | 1994-07-08 | 1996-01-17 | Moli Energy (1990) Limited | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| US5698340A (en) * | 1995-03-03 | 1997-12-16 | Moli Energy (1990) Limited | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| EP0762522A1 (en) * | 1995-08-18 | 1997-03-12 | PETOCA, Ltd | Boron containing carbon material for lithium secondary battery and process for producing the same |
| KR100273710B1 (en) * | 1995-08-18 | 2000-12-15 | 가타야마 노부오 | Carbon material for lithium secondary battery and process for producing the same |
| WO1998024134A1 (en) * | 1996-11-26 | 1998-06-04 | Kao Corporation | Negative electrode material for nonaqueous secondary battery |
| JPH10233208A (en) * | 1996-12-20 | 1998-09-02 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| US6489026B1 (en) | 1999-03-25 | 2002-12-03 | Showa Denko K.K. | Carbon fiber, method for producing the same and electrode for cell |
| US6946110B2 (en) | 1999-03-25 | 2005-09-20 | Showa Denko K.K. | Carbon fibers, production process therefor and electrode for batteries |
| EP1117141A1 (en) * | 1999-07-21 | 2001-07-18 | Mitsubishi Materials Corporation | Carbon powder having enhanced electrical characteristics and use of the same |
| EP1117141A4 (en) * | 1999-07-21 | 2007-02-21 | Mitsubishi Materials Corp | Carbon powder having enhanced electrical characteristics and use of the same |
| US6355377B1 (en) | 2000-03-07 | 2002-03-12 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and method of preparing same |
| WO2002093666A1 (en) * | 2001-05-15 | 2002-11-21 | Fdk Corporation | Nonaqueous electrolytic secondary battery and method of producing anode material thereof |
| US7238449B2 (en) | 2001-05-15 | 2007-07-03 | Fdk Corporation | Nonaqueous electrolytic secondary battery and method of producing anode material thereof |
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