JP2009004148A - Negative electrode for nonaqueous secondary battery, and nonaqueous secondary battery using the same - Google Patents
Negative electrode for nonaqueous secondary battery, and nonaqueous secondary battery using the same Download PDFInfo
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- JP2009004148A JP2009004148A JP2007162242A JP2007162242A JP2009004148A JP 2009004148 A JP2009004148 A JP 2009004148A JP 2007162242 A JP2007162242 A JP 2007162242A JP 2007162242 A JP2007162242 A JP 2007162242A JP 2009004148 A JP2009004148 A JP 2009004148A
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- 239000002245 particle Substances 0.000 claims abstract description 66
- 239000007773 negative electrode material Substances 0.000 claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000000470 constituent Substances 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000004020 conductor Substances 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 23
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
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- 238000000034 method Methods 0.000 description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- -1 organic acid salt Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
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- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- ODEXXNNMGSAXBF-UHFFFAOYSA-N diethyl carbonate;ethyl methyl carbonate Chemical compound CCOC(=O)OC.CCOC(=O)OCC ODEXXNNMGSAXBF-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- GVQPPWPRLCJJOG-UHFFFAOYSA-N dimethyl carbonate;ethyl methyl carbonate Chemical compound COC(=O)OC.CCOC(=O)OC GVQPPWPRLCJJOG-UHFFFAOYSA-N 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
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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
Abstract
Description
本発明は、リチウムイオン二次電池等の非水二次電池及びその負極材料に関する。 The present invention relates to a nonaqueous secondary battery such as a lithium ion secondary battery and a negative electrode material thereof.
従来の非水二次電池は、例えば特許文献１に開示されている。この非水二次電池は非水系の電解質内にリチウムイオンを吸蔵及び脱離できる正極及び負極が浸漬される。負極材料はリチウムバナジウム酸化物から成っている。このリチウムバナジウム酸化物は水酸化リチウム等のリチウム供給源と三酸化バナジウム等のバナジウム供給源とを固相法により混合し、６５０℃以上で焼成して形成される。
A conventional non-aqueous secondary battery is disclosed in
非水二次電池の充電時には負極が負に帯電し、正極に吸蔵されたリチウムイオンが脱離して負極に吸蔵される。非水二次電池の放電時には負極に吸蔵されたリチウムイオンが脱離して正極に吸蔵される。 When the non-aqueous secondary battery is charged, the negative electrode is negatively charged, and lithium ions stored in the positive electrode are desorbed and stored in the negative electrode. At the time of discharging the non-aqueous secondary battery, lithium ions stored in the negative electrode are desorbed and stored in the positive electrode.
従来の非水二次電池用負極において、負極活物質粒子と導電性材料等の負極構成材料粒子との界面にはバインダーが存在したり予め空隙が形成されるなどして、その界面抵抗が高いため、二次電池の容量の低下の要因となっていた。また、充放電サイクルを繰り返すことにより、負極活物質粒子は膨張／収縮を繰り返すため、界面により大きな空隙が形成され、充放電サイクルが進むほど、非水二次電池の容量がさらに低下するという問題があった。 In conventional negative electrodes for non-aqueous secondary batteries, the interface resistance between the negative electrode active material particles and the negative electrode constituent material particles such as the conductive material is high because of the presence of a binder or the formation of voids in advance. Therefore, the capacity of the secondary battery is reduced. Further, since the negative electrode active material particles repeat expansion / contraction by repeating the charge / discharge cycle, a large gap is formed at the interface, and the capacity of the non-aqueous secondary battery further decreases as the charge / discharge cycle progresses. was there.
本発明は、負極活物質と導電性材料等の負極構成材料粒子との導電性経路を十分に確保することによって充放電サイクルが進行しても導電性が低下することを抑制することができる非水二次電池用負極および高い充放電特性を有する非水二次電池を提供することを目的とする。 The present invention can suppress a decrease in conductivity even when a charge / discharge cycle proceeds by sufficiently securing a conductive path between the negative electrode active material and negative electrode constituent material particles such as a conductive material. An object is to provide a negative electrode for a water secondary battery and a non-aqueous secondary battery having high charge / discharge characteristics.
上記目的を達成するため、本発明の発明者らは鋭意検討の結果、負極活物質粒子と導電性材料等の負極高請求項材料粒子とを単純に混合した場合には、導電性経路が不十分であり充放電の繰り返しにより結晶構造が崩壊し、さらなる導電性経路消滅につながり特性が劣化するものと考え、本発明に至った。 In order to achieve the above object, the inventors of the present invention have conducted intensive studies, and as a result, when the negative electrode active material particles and the negatively charged material particles such as the conductive material are simply mixed, the conductive path is not satisfactory. It was considered sufficient and the crystal structure collapsed due to repeated charge and discharge, leading to further disappearance of the conductive path, leading to the deterioration of the characteristics, leading to the present invention.
本発明は、リチウムの挿入、脱離が可能な負極活物質粒子と、前記負極活物質粒子とは異なる負極構成材料粒子とを少なくとも備える非水二次電池用負極において、前記負極活物質粒子および前記負極構成材料粒子のうち少なくともいずれかの粒子表面、前記負極活物質粒子と前記負極構成材料粒子との粒子界面に、Ｌｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上の元素を含む化合物を存在させたことを特徴とする。 The present invention provides a negative electrode for a non-aqueous secondary battery comprising at least negative electrode active material particles capable of inserting and desorbing lithium, and negative electrode constituent material particles different from the negative electrode active material particles. One or more elements of Li, B, Mg, Bi, F, and P are added to the particle surface of at least one of the negative electrode constituent material particles and the particle interface between the negative electrode active material particles and the negative electrode constituent material particles. It is characterized by the presence of a compound containing it.
また本発明は、前記化合物は、前記負極活物質粒子および前記負極構成材料粒子と混合された後に、不活性ガス雰囲気中で焼成されたものであることを特徴とする。 In the invention, it is preferable that the compound is fired in an inert gas atmosphere after being mixed with the negative electrode active material particles and the negative electrode constituent material particles.
また本発明の非水二次電池は、上記各構成の非水二次電池負極材料からなる負極と、正極と、電解質とから成ることを特徴としている。 The non-aqueous secondary battery of the present invention is characterized by comprising a negative electrode made of a non-aqueous secondary battery negative electrode material having the above-described configuration, a positive electrode, and an electrolyte.
本発明によると、負極活物質と、負極活物質とは異なる導電性材料等の負極構成材料とを備える非水二次電池用負極において、負極活物質、負極構成材料のうちいずれかの粒子表面と、負極活物質と負極構成材料との粒子界面にＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上の元素を含む化合物を存在させたことによって、Ｌｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの化合物が、負極活物質粒子同士あるいは、負極活物質粒子、負極構成材料粒子が接触する間の粒子間結合力を高めることができる。したがって、各粒子間の結合力が向上し、その結果として結合した粒子間の接触が強固になり導電性経路を確保できる。更に本発明の技術を用いる効果として、本発明材料を用いた電池の充放電を繰り返した際、負極活物質の膨張／収縮が発生したとしても、負極構成材料粒子間をＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの化合物が強固に結合させている為に膨張／収縮を抑制でき、各材質粒子間の導電性低下を抑制できることから、非水二次電池の充放電特性を向上させることが出来る。 According to the present invention, in a negative electrode for a non-aqueous secondary battery comprising a negative electrode active material and a negative electrode constituent material such as a conductive material different from the negative electrode active material, the surface of any one of the negative electrode active material and the negative electrode constituent material And the presence of a compound containing one or more of Li, B, Mg, Bi, F, and P at the particle interface between the negative electrode active material and the negative electrode constituent material, Li, B, Mg, Bi, The compound of F and P can increase the bonding force between particles while the negative electrode active material particles or the negative electrode active material particles and the negative electrode constituent material particles are in contact with each other. Accordingly, the bonding force between the particles is improved, and as a result, the contact between the bonded particles is strengthened and a conductive path can be secured. Furthermore, as an effect of using the technology of the present invention, even when the battery using the material of the present invention is repeatedly charged and discharged, even if the negative electrode active material expands / shrinks, the anode constituent material particles are intercalated between Li, B, Mg, Since the compound of Bi, F, and P is firmly bonded, expansion / contraction can be suppressed, and the decrease in conductivity between the material particles can be suppressed, so that the charge / discharge characteristics of the non-aqueous secondary battery can be improved. I can do it.
以下に本発明の実施形態を図面を参照して説明する。図３は一実施形態の非水二次電池を示す縦断面図である。非水二次電池１はスパイラル式円筒型のリチウム二次電池から成る。非水二次電池１にはセンターピン６が設けられ、正極３と負極４との間にセパレータ５が挟まれて成る積層体１０がセンターピン６に多重に巻かれている。これにより、積層体１０は円筒状構造を成している。
Embodiments of the present invention will be described below with reference to the drawings. FIG. 3 is a longitudinal sectional view showing a nonaqueous secondary battery according to an embodiment. The non-aqueous
正極３は正極活物質を含む正極合材３ａにより正極集電体３ｂの表面及び裏面の２層を挟んで形成される。負極４は負極活物質を含む負極合材４ａにより負極集電体４ｂの表面及び裏面の２層を挟んで形成される。円筒状の積層体１０は中空円柱状のケース２内に収納され、電解質（不図示）に浸漬されている。ケース２によって正極３が接続されるとともに下端が突出した正極端子７が形成されている。
The
積層体１０の上下にはそれぞれ絶縁板９ｂ、９ａが設けられる。正極集電体３ｂは、絶縁板９ａを貫通して正極リード１１により正極端子７に接続されている。ケース２の開口側の絶縁板９ｂ上には、絶縁板９ｂ方向に凸形状を有する安全弁１３が設けられる。安全弁１３の上方には、安全弁１３とは反対方向に凸形状を有するキャップ状の負極端子８が形成されている。負極集電体４ｂは絶縁板９ｂを貫通して負極リード１２により負極端子８に接続されている。また、安全弁１３及び負極端子８の縁面はガスケット１４によりシールされ、正極端子７から離間している。
正極活物質及び電解質には非水二次電池の正極活物質及び電解質として公知の材料が用いられる。例えば、正極活物質にはコバルト酸リチウム等のリチウム遷移金属酸化物が用いられる。 As the positive electrode active material and the electrolyte, known materials are used as the positive electrode active material and the electrolyte of the non-aqueous secondary battery. For example, a lithium transition metal oxide such as lithium cobalt oxide is used for the positive electrode active material.
また、電解質には非プロトン性溶媒に、リチウム塩から成る溶質を含有したものが用いられる。
非プロトン性溶媒は、環状カ−ボネ−ト単独あるいは鎖状カ−ボネ−トと混合使用されるのが一般だが、混合する場合、次の組合せ例を挙げることができる。エチレンカ−ボネ−トとジメチルカ−ボネ−ト、エチレンカ−ボネ−トとメチルエチルカ−ボネ−ト、エチレンカ−ボネ−トとジエチルカ−ボネ−ト、プロピレンカ−ボネ−トとジメチルカ−ボネ−ト、プロピレンカ−ボネ−トとメチルエチルカ−ボネ−ト、プロピレンカ−ボネ−トとジエチルカ−ボネ−ト、エチレンカ−ボネ−トとプロピレンカ−ボネ−トとジメチルカ−ボネ−ト、エチレンカ−ボネ−トとプロピレンカ−ボネ−トとメチルエチルカ−ボネ−ト、エチレンカ−ボネ−トとプロピレンカ−ボネ−トとジエチルカ−ボネ−ト、エチレンカ−ボネ−トとジメチルカ−ボネ−トとメチルエチルカ−ボネ−ト、エチレンカ−ボネ−トとジメチルカ−ボネ−トとジエチルカ−ボネ−ト、エチレンカ−ボネ−トとメチルエチルカ−ボネ−トとジエチルカ−ボネ−ト、エチレンカ−ボネ−トとジメチルカ−ボネ−トとメチルエチルカ−ボネ−トとジエチルカ−ボネ−ト、エチレンカ−ボネ−トとプロピレンカ−ボネ−トとジメチルカ−ボネ−トとメチルエチルカ−ボネ−ト、エチレンカ−ボネ−トとプロピレンカ−ボネ−トとジメチルカ−ボネ−トとジエチルカ−ボネ−ト、エチレンカ−ボネ−トとプロピレンカ−ボネ−トとメチルエチルカ−ボネ−トとジエチルカ−ボネ−ト、エチレンカ−ボネ−トとプロピレンカ−ボネ−トとジメチルカ−ボネ−トとメチルエチルカ−ボネ−トとジエチルカ−ボネ−ト。
As the electrolyte, an aprotic solvent containing a solute composed of a lithium salt is used.
The aprotic solvent is generally used alone or in combination with a cyclic carbonate, but when mixed, the following combination examples can be given. Ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene Carbonate and methyl ethyl carbonate, propylene carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate and dimethyl carbonate, ethylene carbonate, Propylene carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and diethyl carbonate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, Ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate And diethyl carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate and dimethyl carbonate Methyl ethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl ethyl carbonate Diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate.
環状カ−ボネ−トと鎖状カ−ボネ−トとの混合割合（環状カ−ボネ−ト：鎖状カ−ボネ−ト）は、重量比で表して、好ましくは１：９９〜９９：１、より好ましくは５：９５〜７０：３０、さらに好ましくは１０：９０〜６０：４０である。この混合割合はリチウム二次電池の充放電特性を損なわない非水電解質の良好な電気伝導性をもって適宜決定される。 The mixing ratio of the cyclic carbonate and the chain carbonate (cyclic carbonate: chain carbonate) is preferably expressed by weight ratio, preferably 1:99 to 99: 1, More preferably, it is 5: 95-70: 30, More preferably, it is 10: 90-60: 40. This mixing ratio is appropriately determined with good electrical conductivity of the nonaqueous electrolyte that does not impair the charge / discharge characteristics of the lithium secondary battery.
一方、リチウム塩には、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、Ｌｉ２ＳｉＦ６、ＬｉＯＳＯ２ＣｋＦ（２ｋ＋１）（ｋ＝１〜８の整数）、ＬｉＰＦｎ｛ＣｋＦ（２ｋ＋１）｝（６−ｎ）（ｎ＝１〜５の整数、ｋ＝１〜８の整数）、ＬｉＢＯＢ（リチウムビス（オキサラート）ボレート）、ＬｉＢＥＴＩ（リチウムビス（パーフルオロエタンスルホニル）イミド）などのリチウム塩が挙げられる。また、次の一般式で示されるリチウム塩も使用することができる。ＬｉＣ（ＳＯ２Ｒ５）（ＳＯ２Ｒ６）（ＳＯ２Ｒ７）、ＬｉＮ（ＳＯ２ＯＲ８）（ＳＯ２ＯＲ９）、ＬｉＮ（ＳＯ２Ｒ１０）（ＳＯ２ＯＲ１１）、ＬｉＮ（ＳＯ２Ｒ１２）（ＳＯ２Ｒ１３）。ここで、Ｒ５〜Ｒ１３は、互いに同一であってもよいし異なっていてもよく、炭素数１〜８のパ−フルオロアルキル基である。これらのリチウム塩は単独で使用してもよいし、また２種類以上を混合して使用してもよい。
また、本発明の負極材料界面に存在するＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの化合物が酸に溶解し、電池特性を劣化させる場合は、上記リチウム塩の使用においてＨＦの発生を抑制できる塩が好ましい。
また、従来技術で適用される添加剤（ビニレンカーボネート、フルオロエチレンカーボネート等）を添加してもよい。
On the other hand, lithium salt includes LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , Li 2 SiF 6 , LiOSO 2 C k F (2k + 1) (k = 1 to 8), LiPF n {C k F (2k + 1) ) } (6-n) (n = 1 to 5 integer, k = 1 to 8 integer), LiBOB (lithium bis (oxalate) borate), LiBETI (lithium bis (perfluoroethanesulfonyl) imide) and other lithium Salt. Moreover, the lithium salt shown by the following general formula can also be used. LiC (SO 2 R 5 ) (SO 2 R 6 ) (SO 2 R 7 ), LiN (SO 2 OR 8 ) (SO 2 OR 9 ), LiN (SO 2 R 10 ) (SO 2 OR 11 ), LiN ( SO 2 R 12) (SO 2 R 13). Here, R 5 to R 13 may be the same as or different from each other, and are a C 1-8 perfluoroalkyl group. These lithium salts may be used alone or in combination of two or more.
In addition, when the Li, B, Mg, Bi, F, and P compounds present at the negative electrode material interface of the present invention are dissolved in an acid and deteriorate the battery characteristics, generation of HF can be suppressed in the use of the lithium salt. Salts are preferred.
Moreover, you may add the additives (vinylene carbonate, fluoroethylene carbonate, etc.) applied with a prior art.
負極４は、負極活物質と導電性材料等の負極構成材料とにより構成される。負極活物質としては、リチウムと合金化が可能な金属質物単体やリチウムの吸蔵、放出が可能なＬｉを含んだＶ化合物、Ｍｎ化合物、Ｆｅ化合物、Ｖ酸化物、Ｍｎ酸化物、Ｆｅ酸化物Ｖ硫化物、Ｍｎ硫化物、Ｆｅ硫化物を挙げることができ、含まれる金属としては、例えば、Ｍｇ、Ｔｉ、Ａｌ、Ｚｒ等、少なくとも一種類以上含む物質を例示できる。リチウムと合金化が可能な金属としては、Ｓｉ、Ａｌ、Ｓｎ、Ｐｂ、Ｚｎ、Ｂｉ、Ｉｎ、Ｍｇ、Ｇａ、Ｃｄ等を例示できる。前記金属質物と複合化する炭素質材料としては、人造黒鉛、天然黒鉛、黒鉛化炭素繊維、黒鉛化メソカーボンマイクロビーズ、非晶質炭素等を例示できる。また、導電性材料としてはカーボンブラック、黒鉛粉末、炭素繊維、金属粉末、金属繊維等があげられる。
The
本発明の負極４においては、負極活物質粒子と、他の負極構成材料粒子との粒子界面といずれかの材料の粒子表面とにＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上を含む化合物が存在するようになっている。そして、該負極活物質９６％、アセチレンブラック２％、バインダー２％を混合して銅から成る負極集電体３ｂ上に塗布し、１．８ｇ／ｃｍ３となるようにプレス加工して形成されている。
In the
例えば、主たる負極活物質としてリチウムバナジウム酸化物を用いる場合には、負極４はリチウムバナジウム酸化物および黒鉛等の他の負極活物質と、アセチレンブラック等の導電性材料とを含み構成される。
For example, when lithium vanadium oxide is used as the main negative electrode active material, the
このリチウムバナジウム酸化物は、ＬｉａＶｂＭｃＯｄの一般式により表されるものである。ここで、ａ，ｂ，ｃ，ｄは任意の数値であり、Ｍは遷移金属、アルカリ金属、アルカリ土類金属の中から選ばれる少なくとも一種あるいは複数の元素である。製法としては、例えば、ＬｉＯＨとＶ２Ｏ３とを原料としてＭを添加し所定温度で焼成する方法（乾式法）や、Ｌｉ２ＣＯ３とＶ２Ｏ５とＭと有機酸とを混合して得られる有機酸塩を所定温度で焼成する方法（湿式法）が挙げられる。尚、湿式法は使用される原料が比較的安価であるため、工業化においてより好ましい。なお、炭酸リチウム、五酸化バナジウム及びシュウ酸を用いた場合には、特に安価で容易に上記有機酸塩を得ることができる。リチウム化合物として、水酸化リチウム、蓚酸リチウムなどを用いてもよい。還元剤として、有機酸、カーボン材料、過酸化水素などを用いてもよい。 This lithium vanadium oxide is represented by the general formula of Li a V b M c O d . Here, a, b, c, and d are arbitrary numerical values, and M is at least one element selected from transition metals, alkali metals, and alkaline earth metals. As a manufacturing method, for example, a method in which M is added using LiOH and V 2 O 3 as raw materials and baked at a predetermined temperature (dry method), or Li 2 CO 3 , V 2 O 5 , M, and an organic acid are mixed. And a method (wet method) of firing the organic acid salt obtained at a predetermined temperature. In addition, since the raw material used is comparatively cheap, the wet method is more preferable in industrialization. In addition, when lithium carbonate, vanadium pentoxide, and oxalic acid are used, the organic acid salt can be easily obtained particularly at low cost. As the lithium compound, lithium hydroxide, lithium oxalate, or the like may be used. As the reducing agent, an organic acid, a carbon material, hydrogen peroxide, or the like may be used.
負極を構成する材料中にＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上を含む化合物を存在させる方法としては、例えば、リチウムバナジウム酸化物と、他の負極活物質および／または導電性材料と、Ｌｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上を含んだ化合物とを混合し、不活性ガス雰囲気中で焼成する方法がある。また、リチウムバナジウム酸化物、他の負極活物質および／または導電性材料の表面にＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上を含んだ化合物を予め点在させてからリチウムバナジウム酸化物と、他の負極活物質および／または導電性材料を混合し、不活性ガス雰囲気中で焼成するのでもよい。 Examples of a method for causing a compound containing one or more of Li, B, Mg, Bi, F, and P to be present in the material constituting the negative electrode include, for example, lithium vanadium oxide, other negative electrode active materials, and / or conductive materials. There is a method in which a reactive material and a compound containing one or more of Li, B, Mg, Bi, F, and P are mixed and fired in an inert gas atmosphere. In addition, a lithium vanadium oxide, another negative electrode active material and / or a surface of a conductive material is preliminarily dotted with a compound containing one or more of Li, B, Mg, Bi, F, and P, and then lithium vanadium. The oxide may be mixed with another negative electrode active material and / or a conductive material, and fired in an inert gas atmosphere.
また、負極を構成する材料中にＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上を含む化合物を存在させる方法としては、リチウム化合物として炭酸リチウム（Ｌｉ２ＣＯ３）、バナジウム化合物として五酸化バナジウム（Ｖ２Ｏ５）、還元剤とシュウ酸を混合して水溶液中において反応させ乾燥させた後に、Ｌｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上を含む化合物と黒鉛とを混合し、焼成して得る方法もある。この方法によれば、Ｌｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上を含む化合物が均一に分散することが可能である。
なお、上記化合物は、炭酸塩、水酸化物、酸化物などである。
また、不活性ガスとしては、窒素、窒素と水素の混合ガス、またはアルゴンガスなどが挙げられる。
In addition, as a method for causing a compound containing one or more of Li, B, Mg, Bi, F, and P to be present in the material constituting the negative electrode, lithium carbonate (Li 2 CO 3 ) as a lithium compound, vanadium compound as A compound containing one or more of Li, B, Mg, Bi, F, P and graphite after mixing vanadium pentoxide (V 2 O 5 ), a reducing agent and oxalic acid, reacting in an aqueous solution and drying. There is also a method obtained by mixing and baking. According to this method, a compound containing at least one of Li, B, Mg, Bi, F, and P can be uniformly dispersed.
In addition, the said compound is carbonate, a hydroxide, an oxide, etc.
Examples of the inert gas include nitrogen, a mixed gas of nitrogen and hydrogen, or argon gas.
この負極によれば、リチウムバナジウム酸化物はリチウムバナジウム酸化物以外の負極材料または導電性材料との伝導経路を確保できるだけでなく、リチウムバナジウム酸化物粒子間、その他の負極活物質間の導電性経路も確保できる。従って、伝導性の良好なリチウムバナジウム酸化物を含有する負極を得ることができ、非水二次電池の容量向上、サイクル特性の向上に効果が期待できる。 According to this negative electrode, lithium vanadium oxide can not only secure a conduction path with a negative electrode material or conductive material other than lithium vanadium oxide, but also between lithium vanadium oxide particles and other negative electrode active materials. Can also be secured. Therefore, a negative electrode containing a lithium vanadium oxide having good conductivity can be obtained, and an effect can be expected for improving the capacity and cycle characteristics of the nonaqueous secondary battery.
次に、本発明において実施した実施形態及びその比較の製造方法を参照しつつ、本発明の実施の形態についてさらに詳細に説明する。 Next, the embodiment of the present invention will be described in more detail with reference to the embodiment implemented in the present invention and the comparative manufacturing method.
（実施例１）
炭酸リチウム２０８ｇ、五酸化バナジウム４２５ｇとシュウ酸をイオン交換水５Ｌに所定の割合添加し、６０度の条件化で溶解させた。この溶液を前駆体溶液とし、窒素雰囲気中１１００度で焼成することでリチウムバナジウム酸化物を得ることができる。得られたリチウムバナジウム酸化物と添加化合物としてＢ２Ｏ３（リチウムバナジウム酸化物に対して０.５ｗｔ％）、黒鉛粒子（リチウムバナジウム酸化物/黒鉛粒子＝８０：２０ｗｔ％）を混合して窒素雰囲気中で焼成した。このようにしてリチウムバナジウム酸化物、黒鉛の表面および界面にリチウム化合物を含む負極材料を得ることができた。
(Example 1)
A predetermined ratio of 208 g of lithium carbonate, 425 g of vanadium pentoxide and oxalic acid was added to 5 L of ion-exchanged water, and dissolved under conditions of 60 degrees. Lithium vanadium oxide can be obtained by using this solution as a precursor solution and firing at 1100 degrees in a nitrogen atmosphere. The resulting lithium vanadium oxide was mixed with B 2 O 3 (0.5 wt% with respect to the lithium vanadium oxide) and graphite particles (lithium vanadium oxide / graphite particles = 80: 20 wt%) as an additive compound to form nitrogen. Baking in the atmosphere. In this way, a negative electrode material containing a lithium compound on the surface and interface of lithium vanadium oxide and graphite could be obtained.
得られた負極材料とアセチレンブラック、ポリフッ化ビニリデン（ｐｖｄｆ）とを９６：２：２の重量割合で混合しＮ−メチル−２−ピロリドンを添加してスラリーを作製した。作製したスラリーを銅箔に塗布し、乾燥後、電極密度を１．８ｇ／ｃｍ３として負極電極とした。正極電極は、コバルト酸リチウムを、電解液には、エチルカーボネート（ＥＣ）：ジエチルカーボネート（ＤＥＣ）＝３：７の溶媒に１．４ＭのＬｉＰＦ６を溶解させたものを用いて非水二次電池を作製した。 The obtained negative electrode material, acetylene black, and polyvinylidene fluoride (pvdf) were mixed at a weight ratio of 96: 2: 2, and N-methyl-2-pyrrolidone was added to prepare a slurry. The prepared slurry was applied to a copper foil, and after drying, the electrode density was 1.8 g / cm 3 to obtain a negative electrode. The positive electrode is lithium cobaltate, and the electrolyte is non-aqueous secondary using 1.4M LiPF 6 dissolved in a solvent of ethyl carbonate (EC): diethyl carbonate (DEC) = 3: 7. A battery was produced.
（実施例２）
添加化合物をＬｉＯＨ・Ｈ２Ｏとした以外、実施例１と同様な方法で負極材料の合成を行ない、非水二次電池を作製した。
(Example 2)
A negative electrode material was synthesized in the same manner as in Example 1 except that the additive compound was LiOH.H 2 O, and a non-aqueous secondary battery was produced.
（実施例３）
添加化合物をＢｉ２Ｏ３とした以外、実施例１と同様な方法で負極材料の合成を行ない、非水二次電池を作製した。
(Example 3)
A negative electrode material was synthesized in the same manner as in Example 1 except that the additive compound was Bi 2 O 3 to produce a nonaqueous secondary battery.
（実施例４）
添加化合物をＬｉＦとした以外、実施例１と同様な方法で負極材料の合成を行ない、非水二次電池を作製した。
Example 4
A negative electrode material was synthesized in the same manner as in Example 1 except that the additive compound was LiF, to produce a nonaqueous secondary battery.
（実施例５）
添加化合物をＰ２Ｏ５とした以外、実施例１と同様な方法で負極材料の合成を行ない、非水二次電池を作製した。
(Example 5)
A negative electrode material was synthesized in the same manner as in Example 1 except that the additive compound was P 2 O 5 to produce a non-aqueous secondary battery.
（実施例６）
炭酸リチウム２０８ｇ、五酸化バナジウム４２５ｇとシュウ酸をイオン交換水５Ｌに所定の割合添加し、６０度の条件化で溶解させた。この溶液を乾燥し前駆体とし、黒鉛粒子（リチウムバナジウム酸化物/黒鉛粒子＝２０：８０ｗｔ％）とＢ２Ｏ３（リチウムバナジウム酸化物に対して０．５ｗｔ％）を添加し、窒素雰囲気中１１００度で焼成することでリチウムバナジウム酸化物、黒鉛の表面および界面にホウ素化合物を含む負極材料を得ることができた。電池の構成においては、実施例１と同様にして実施した。
(Example 6)
A predetermined ratio of 208 g of lithium carbonate, 425 g of vanadium pentoxide and oxalic acid was added to 5 L of ion-exchanged water, and dissolved under conditions of 60 degrees. This solution is dried to be a precursor, graphite particles (lithium vanadium oxide / graphite particles = 20: 80 wt%) and B 2 O 3 (0.5 wt% with respect to lithium vanadium oxide) are added, and in a nitrogen atmosphere A negative electrode material containing a boron compound on the surface and interface of lithium vanadium oxide and graphite could be obtained by firing at 1100 degrees. The battery configuration was the same as in Example 1.
（実施例７）
添加化合物をＢｉ２Ｏ３とした以外、実施例６と同様な方法で負極材料の合成を行ない、非水二次電池を作製した。
(Example 7)
A negative electrode material was synthesized in the same manner as in Example 6 except that the additive compound was Bi 2 O 3 to produce a non-aqueous secondary battery.
（実施例８）
添加化合物をＰ２Ｏ５とした以外、実施例６と同様な方法で負極材料の合成を行ない、非水二次電池を作製した。
(Example 8)
A negative electrode material was synthesized in the same manner as in Example 6 except that the additive compound was P 2 O 5 to produce a non-aqueous secondary battery.
続いて、比較例１から２の製造方法について説明する。
（比較例１）
炭酸リチウム２０８ｇと五酸化バナジウム４２５ｇとシュウ酸１２１８ｇを添加した溶液を１３０℃の定置乾燥機で乾燥させ、その後窒素雰囲気で１１００℃で焼成を行った。得られたリチウムバナジウム酸化物と黒鉛粒子を重量割合で８０/２０となるように混合し負極材料とし、負極材料とアセチレンブラック、ｐｖｄｆとを９６：２：２の重量割合で混合しＮ−メチル−２−ピロリドンを添加してスラリーを作製した。
また、作製したスラリーを銅箔に塗布し、乾燥後、電極密度を１．８ｇ／ｃｍ３として負極電極とした。正極電極は、コバルト酸リチウムを、電解液には、エチルカーボネート（ＥＣ）：ジエチルカーボネート（ＤＥＣ）＝３：７の溶媒に１．４ＭのＬｉＰＦ６を溶解させたものを用いて非水二次電池を作製した。
Then, the manufacturing method of Comparative Examples 1 and 2 is demonstrated.
(Comparative Example 1)
A solution added with 208 g of lithium carbonate, 425 g of vanadium pentoxide and 1218 g of oxalic acid was dried with a stationary dryer at 130 ° C., and then fired at 1100 ° C. in a nitrogen atmosphere. The obtained lithium vanadium oxide and graphite particles were mixed to a weight ratio of 80/20 to form a negative electrode material, and the negative electrode material, acetylene black, and pvdf were mixed in a weight ratio of 96: 2: 2 to obtain N-methyl. 2-Pyrrolidone was added to make a slurry.
Moreover, the produced slurry was apply | coated to copper foil, and after drying, the electrode density was set to 1.8 g / cm < 3 > and it was set as the negative electrode. The positive electrode is lithium cobaltate, and the electrolyte is non-aqueous secondary using 1.4M LiPF 6 dissolved in a solvent of ethyl carbonate (EC): diethyl carbonate (DEC) = 3: 7. A battery was produced.
（比較例２）
焼成温度のみ９５０度とした以外、比較例１と同様に合成を行い、非水二次電池を作製した。
(Comparative Example 2)
A non-aqueous secondary battery was produced in the same manner as in Comparative Example 1 except that only the firing temperature was 950 degrees.
次に、このようにして得られたリチウム二次電池用負極材料を評価した結果について説明する。
表１は、実施例１から８と比較例１から２の実験結果を表す一覧表である。
Next, the result of evaluating the negative electrode material for a lithium secondary battery obtained in this manner will be described.
Table 1 is a list showing the experimental results of Examples 1 to 8 and Comparative Examples 1 and 2.
評価項目として、１サイクル目の容量を１００とした場合の、１００サイクル後の容量維持率（％）を採用した。ここでは、容量維持率（％）は、８０％以上であれば良好といえる。
実施例１において添加元素Ｌｉの場合で８９％の維持率を示し、実施例２において添加元素Ｂの場合で８３％の維持率を示し、実施例３において添加元素Ｂｉの場合で８３％の維持率を示し、実施例４において添加元素Ｆの場合で８９％の維持率をしめし、実施例５において添加元素Ｐの場合で８８％の維持率を示す。このように添加元素を変更させた場合でも、１００サイクル後の容量維持率が８０％以上であることが確認できる。
As an evaluation item, the capacity retention rate (%) after 100 cycles when the capacity at the first cycle was set to 100 was adopted. Here, it can be said that the capacity retention rate (%) is good if it is 80% or more.
In Example 1, the retention rate of 89% was exhibited in the case of the additive element Li, 83% was maintained in the case of the additive element B in Example 2, and 83% was maintained in the case of the additive element Bi in Example 3. In Example 4, the retention rate is 89% in the case of the additive element F, and in Example 5, the retention rate is 88% in the case of the addition element P. Even when the additive element is changed in this way, it can be confirmed that the capacity retention rate after 100 cycles is 80% or more.
比較例は、Ｌｉ、Ｂ、Ｂｉ、Ｆ、Ｐの化合物を添加せず、リチウムバナジウム酸化物と黒鉛を混合した。また、焼成温度を変えることで、リチウムバナジウム酸化物の粒子サイズを変更している。１００サイクル後の容量維持率は、比較例１で６８％、比較例２で６２％、であり、単純に混合しただけでは、黒鉛とリチウムバナジウム酸化物とが、単独で存在するに過ぎず、接触抵抗が増加し容量維持率が低下したものと推察される。 In the comparative example, lithium vanadium oxide and graphite were mixed without adding Li, B, Bi, F, and P compounds. Moreover, the particle size of the lithium vanadium oxide is changed by changing the firing temperature. The capacity maintenance ratio after 100 cycles is 68% in Comparative Example 1 and 62% in Comparative Example 2, and simply mixing graphite and lithium vanadium oxide alone exists, It is inferred that the contact resistance increased and the capacity retention rate decreased.
このように、本発明によれば、負極活物質と、負極活物質とは異なる導電性材料等の負極構成材料とを備える非水二次電池用負極において、負極活物質、負極構成材料のうちいずれかの粒子表面と、負極活物質と負極構成材料との粒子界面にＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上の元素を含む化合物を存在させたことによって、Ｌｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの化合物が、負極活物質粒子同士あるいは、負極活物質粒子、負極構成材料粒子が接触する間の粒子間結合力を高めることができる。したがって、各粒子間の結合力が向上し、その結果として結合した粒子間の接触が強固になり導電性経路を確保できる。更に本発明の技術を用いる効果として、本発明材料を用いた電池の充放電を繰り返した際、負極活物質の膨張／収縮が発生したとしても、負極構成材料粒子間をＬｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの化合物が強固に結合させている為に膨張／収縮を抑制でき、各材質粒子間の導電性低下を抑制できることから、非水二次電池の充放電特性を向上させることが出来る。 Thus, according to the present invention, in a negative electrode for a non-aqueous secondary battery comprising a negative electrode active material and a negative electrode constituent material such as a conductive material different from the negative electrode active material, The presence of a compound containing one or more elements of Li, B, Mg, Bi, F, and P at the particle surface of any one of the particles and the particle interface between the negative electrode active material and the negative electrode constituent material causes Li, B , Mg, Bi, F, and P can increase the interparticle bonding force during contact between the negative electrode active material particles or between the negative electrode active material particles and the negative electrode constituent material particles. Accordingly, the bonding force between the particles is improved, and as a result, the contact between the bonded particles is strengthened and a conductive path can be secured. Furthermore, as an effect of using the technology of the present invention, even when the battery using the material of the present invention is repeatedly charged and discharged, even if the negative electrode active material expands / shrinks, the anode constituent material particles are intercalated between Li, B, Mg, Since the compound of Bi, F, and P is firmly bonded, expansion / contraction can be suppressed, and the decrease in conductivity between the material particles can be suppressed, so that the charge / discharge characteristics of the non-aqueous secondary battery can be improved. I can do it.
以上、具体例を参照しつつ、本発明の実施形態について説明した。しかし、本発明はこれらの具体例に限定されるのもではない。
例えば、本実施形態の負極活物質を用いるリチウム二次電池は、スパイラル式円筒形のリチウム二次電池に限らず、コイン形のリチウム二次電池や、角形のリチウム二次電池においても本発明の特徴を有する限り同様の効果が得られる。
本実施形態の負極活物質の組成や、それに含まれるＭｅ元素の種類、各構成部材の材質、形状、製造工程、製造条件、リチウム二次電池の形状等の構成に関して、本発明の特徴を有する限り、本発明の範囲に包含される。
The embodiments of the present invention have been described above with reference to specific examples. However, the present invention is not limited to these specific examples.
For example, the lithium secondary battery using the negative electrode active material of the present embodiment is not limited to a spiral cylindrical lithium secondary battery, but also in a coin-type lithium secondary battery or a square lithium secondary battery. The same effect can be obtained as long as it has characteristics.
The composition of the negative electrode active material of the present embodiment, the type of Me element contained therein, the material, shape, manufacturing process, manufacturing conditions of each component, the configuration of the lithium secondary battery, etc. have the features of the present invention. As long as it is within the scope of the present invention.
１ 非水二次電池
２ ケース
３ 正極
４ 負極
５ セパレータ
６ センターピン
７ 正極端子
８ 負極端子
１０ 積層体
DESCRIPTION OF
Claims (3)
前記負極活物質粒子および前記負極構成材料粒子のうち少なくともいずれかの粒子表面、前記負極活物質粒子と前記負極構成材料粒子との粒子界面に、Ｌｉ、Ｂ、Ｍｇ、Ｂｉ、Ｆ、Ｐの内一つ以上の元素を含む化合物を存在させたことを特徴とする非水二次電池用負極。 In a negative electrode for a non-aqueous secondary battery comprising at least negative electrode active material particles capable of inserting and desorbing lithium, and negative electrode constituent material particles different from the negative electrode active material particles,
The surface of at least one of the negative electrode active material particles and the negative electrode constituent material particles, and the particle interface between the negative electrode active material particles and the negative electrode constituent material particles, include Li, B, Mg, Bi, F, and P. A negative electrode for a non-aqueous secondary battery, wherein a compound containing one or more elements is present.
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