JPH03289050A - Manufacture of sintered type nickel positive electrode - Google Patents
Manufacture of sintered type nickel positive electrodeInfo
- Publication number
- JPH03289050A JPH03289050A JP2089500A JP8950090A JPH03289050A JP H03289050 A JPH03289050 A JP H03289050A JP 2089500 A JP2089500 A JP 2089500A JP 8950090 A JP8950090 A JP 8950090A JP H03289050 A JPH03289050 A JP H03289050A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- nickel
- sintered
- active material
- silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000758 substrate Substances 0.000 claims description 19
- 239000003292 glue Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 19
- 230000008961 swelling Effects 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002585 base Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 229910006279 γ-NiOOH Inorganic materials 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、ニッケルーカドミウム電池、ニッケルー水素
電池などの正極に用いられる焼結式ニッケル正極の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for manufacturing a sintered nickel positive electrode used for positive electrodes of nickel-cadmium batteries, nickel-hydrogen batteries, and the like.
（ロ）従来の技術
アルカリ蓄電池に用いられる焼結式ニッケル正極は、一
般に以下の方法によって製造される。(b) Prior Art Sintered nickel positive electrodes used in alkaline storage batteries are generally manufactured by the following method.
まず、ニッケル粉末、糊料及び水を混合してスラリーを
作製し、このスラリーをパンチングメタルなどの芯体に
塗着、乾燥した後、還元性雰囲気中で焼結して多孔性ニ
ッケル焼結基板を得る。次いで、この基板を硝酸ニッケ
ル水溶液などの酸性ニンケル塩溶液に浸漬し、アルカリ
中で中和するなどして、基板中に水酸化ニッケルを充填
する活物質充填操作を数回繰り返すことによって、基板
中に活物質を充填して作製する。First, create a slurry by mixing nickel powder, glue, and water, apply this slurry to a core such as punching metal, dry it, and then sinter it in a reducing atmosphere to create a porous nickel sintered substrate. get. Next, this substrate is immersed in an acidic nickel salt solution such as an aqueous nickel nitrate solution, neutralized in an alkali, etc., and the active material filling operation of filling nickel hydroxide into the substrate is repeated several times. Filled with active material.
こうして作製された焼結式ニッケル正極を使用した密閉
型ニッケルーカドミウム電池では、寿命を決定する要因
として、ドライアウトと呼ばれる電解液の涸渇がある。In the sealed nickel-cadmium battery using the sintered nickel positive electrode manufactured in this way, a factor that determines the lifespan is depletion of the electrolyte called dryout.
また、このドライアウトが生じる原因は、以下の２つに
大きく分けられる。Furthermore, the causes of this dryout can be broadly divided into the following two types.
即ち、その一つは、過充電や過放電の繰り返しによって
発生したガスが電池内に溜って、安全弁が作動し、これ
によって、前記ガスや電解液が電池外に放出され、電池
内の電解液が涸渇して生じるドライアウトである。他の
一つは、正極が膨化することによって、セパレータ内に
保持されていた電解液が絞り出されて正極に保持され、
正、負極間に存在する電解液量が減少して生じるドライ
アウトである。そして、１記正極の膨化は、充放電によ
り正極活物質が、放電状態のＮ１（０１−１）１と充電
状態のＮ ｉ ＯＯＨに交互に変化することで膨張、収
縮を繰り返し、これによって、正極の基体を構成する焼
結金属のマトリックスが切断して生じることが主たる原
因と考えられる。One of them is that the gas generated by repeated overcharging and overdischarging accumulates inside the battery, and the safety valve operates, which releases the gas and electrolyte outside the battery, causing the electrolyte inside the battery to drain. Dryout occurs when the water is depleted. The other is that when the positive electrode expands, the electrolyte held in the separator is squeezed out and retained in the positive electrode.
Dryout occurs when the amount of electrolyte present between the positive and negative electrodes decreases. The expansion of the positive electrode is caused by the positive electrode active material repeatedly expanding and contracting as it alternately changes to N1(01-1)1 in a discharged state and N i OOH in a charged state due to charging and discharging. The main cause is thought to be that the sintered metal matrix that forms the base of the positive electrode is cut.
゛前者の場合は、負極の容量を正極の容量より大きくし
、充電によって正極が満充電になった際に、負極に未充
電部分が残るようにすることなどにより防止できる。こ
の構成を採用することで、過充電時において、電池内で
消費できる酸素ガスを正極から優先的に発生させ、電池
内で消費できない水素ガスを負極から発生させないよう
にでき、ドライアウトの原因である安全弁の作動を防Ｉ
Ｆできる。The former case can be prevented by making the capacity of the negative electrode larger than the capacity of the positive electrode so that when the positive electrode becomes fully charged, an uncharged portion remains on the negative electrode. By adopting this configuration, during overcharging, oxygen gas that can be consumed within the battery can be generated preferentially from the positive electrode, and hydrogen gas that cannot be consumed within the battery can be prevented from being generated from the negative electrode, which can cause dry-out. Preventing the activation of a certain safety valve
F can do it.
他方、後者の場合には、特公昭６０−１２７４２号公報
に提案されているように、正極活物質中にカドミウムを
添加して、正極の膨化を防止することによって抑制でき
る。しかしながら、この方法を採用しても、まだ充分に
正極の膨化を防止することはできなかった。On the other hand, the latter case can be suppressed by adding cadmium to the positive electrode active material to prevent swelling of the positive electrode, as proposed in Japanese Patent Publication No. 60-12742. However, even with this method, it was still not possible to sufficiently prevent the positive electrode from swelling.
（ハ）発明が解決しようとする課題
本発明は、充放電の繰り返しにより正極が膨化すること
を効果的に防止できる長か命のアルカリ蓄電池用の焼結
式ニッケル正極の製造方法を提供しようとするものであ
る。(c) Problems to be Solved by the Invention The present invention seeks to provide a method for manufacturing a sintered nickel positive electrode for a long-life alkaline storage battery that can effectively prevent the positive electrode from swelling due to repeated charging and discharging. It is something to do.
（ニ）課題を解決するための手段
本発明の焼結式ニッケル正極の製造方法は、ニッケル粉
末と糊料とを主体とし、ケイ酸もしくはケイ酸塩を添加
した混合物を焼結して多孔性焼結基板を作製した後、該
基板に酸性ニッケル塩溶液への浸漬を伴う活物質充填操
作を行なうことを特徴とするものである。(d) Means for Solving the Problems The method for producing a sintered nickel positive electrode of the present invention is to sinter a mixture mainly consisting of nickel powder and paste, to which silicic acid or silicate is added, to form a porous nickel positive electrode. The method is characterized in that after a sintered substrate is produced, an active material filling operation involving immersion of the substrate in an acidic nickel salt solution is performed.
（ホ）作用
正極活物質としてのＮｉ０ＯＨには、β型とγ型が存在
し、γ−Ｎ ｉ ＯＯＨはβ−Ｎ ｉ ＯＯＨに比べて
密度が小さく、単位重量当りの体積が大きい。したがっ
て、正極中にγ−Ｎ ｉ ＯＯＨが多く生成する場合に
は、充電時に活物質の膨張によって電極基板を構成する
焼結ニッケルのマトリックスにかかる力も大きくなる。(e) Ni0OH as a functional positive electrode active material has a β type and a γ type, and γ-N i OOH has a lower density and a larger volume per unit weight than β-N i OOH. Therefore, when a large amount of γ-N i OOH is generated in the positive electrode, the force applied to the sintered nickel matrix constituting the electrode substrate also increases due to expansion of the active material during charging.
このため、充放電を繰り返していくと、焼結ニッケルの
マトリックスが切断され、活物質の膨張を基板で吸収で
きなくなって、正極が膨張することになる。Therefore, when charging and discharging are repeated, the sintered nickel matrix is cut, and the expansion of the active material can no longer be absorbed by the substrate, causing the positive electrode to expand.
これに対して、ケイ素またはケイ素塩を含有させた状態
で、ニッケルスラリーを焼結する工程を経て正極を製造
した場合には、充電時にγ−Ｎ１００ Ｈが生成するこ
とを抑制することができる。On the other hand, if the positive electrode is manufactured through a step of sintering nickel slurry while containing silicon or a silicon salt, it is possible to suppress the generation of γ-N100 H during charging.
この理由は定かではないが、以下のことが原因となって
いるものと考えられる。Although the reason for this is not certain, it is thought that the following is the cause.
つまり、ケイ素は他の金属と合金を形成し易いことから
、焼結基板表面層においてニッケルと合金を形成し、焼
結後に引き続き行なう酸性ニッケル塩溶液への浸漬時に
おいて、焼結体の腐食を抑制することができる。焼結基
板に腐食が生じて、基板から溶は出したニッケルが活物
質化した場合には、生成した活物質が充電時にγ−Ｎｉ
ＯＯＨを形成し易いと考えられるが、本発明ではこの腐
食が防止でき、γ−Ｎｉ００Ｈの生成が抑制されるため
、正極の膨化が抑えられたと考えられる。In other words, since silicon easily forms alloys with other metals, it forms an alloy with nickel on the surface layer of the sintered substrate, and prevents corrosion of the sintered body when immersed in an acidic nickel salt solution after sintering. Can be suppressed. If corrosion occurs on the sintered substrate and the nickel dissolved from the substrate becomes an active material, the generated active material becomes γ-Ni during charging.
It is thought that OOH is likely to be formed, but in the present invention, this corrosion can be prevented and the formation of γ-Ni00H is suppressed, so it is thought that swelling of the positive electrode is suppressed.
また、ケイ素は充電時の活物質の結晶構造を制岬するも
ので、ケイ素化合物を含有することで、γ−Ｎｉ００１
１の生成が抑制されることも影響していると考えられる
。In addition, silicon controls the crystal structure of the active material during charging, and by containing silicon compounds, γ-Ni001
It is thought that suppression of the production of 1 also has an effect.
尚、ケイ素化合物の添加量は、５００ ｐｐｍ程度の極
少量で良く、少量添加により、焼結体強度の低ドや、活
物質充填への悪影響及び活物質の利用率の低ドもない。The amount of the silicon compound to be added may be as small as about 500 ppm, and by adding a small amount, there will be no reduction in the strength of the sintered body, an adverse effect on the filling of the active material, and a reduction in the utilization rate of the active material.
（へ）実施例
Ｉ ＮＣＯ社製Ｔｙｐｅ２５５のニッケル粉末と、水及
びセルロース系糊料を混合してスラリーを作製し、この
スラリーを鉄にニッケルメッキを施したパンチングメタ
ルの両面に塗着し、乾燥した後、オルトケイ酸ナトリウ
ム０．２重量％の水溶液を噴霧し、これを還元性雰囲気
で焼結してニッケル焼結基板を作製した。この基板中の
５１量はＮ１喰に対して５００ ｐｐｍであった。(f) Example I A slurry was prepared by mixing Type 255 nickel powder manufactured by NCO, water and cellulose paste, this slurry was applied to both sides of punched metal made of nickel plated iron, and dried. After that, an aqueous solution containing 0.2% by weight of sodium orthosilicate was sprayed, and this was sintered in a reducing atmosphere to produce a nickel sintered substrate. The amount of 51 in this substrate was 500 ppm relative to N1.
次いで、この焼結基板を硝酸ニッケルを主体とする硝酸
塩水溶液に浸漬し、乾燥した後、アルカノ水溶液中に浸
漬するという活物質充填操作を繰リ返１−１ｊなって、
基板中に活物質を充填した。Next, the active material filling operation of immersing this sintered substrate in a nitrate aqueous solution mainly composed of nickel nitrate, drying it, and then immersing it in an alkano aqueous solution was repeated in steps 1-1j.
The active material was filled into the substrate.
尚、活物質組成比はＮ ｉ ： Ｃｏ ：Ｃｄ＝９０
： ５５であり、いずれら水酸化物の形態で充填されて
いる。こうして作製した本発明方法によるニッケル正極
を正極Ａとする。In addition, the active material composition ratio is Ni:Co:Cd=90
: 55, and both are filled in the form of hydroxide. The nickel positive electrode thus produced by the method of the present invention will be referred to as positive electrode A.
また、比較としてオルトケイ酸ナトリウムを添加せず、
その他は前記正極Ａと同様にしてニッケル正極を作製し
、正極Ｂとする。Also, for comparison, without adding sodium orthosilicate,
Otherwise, a nickel positive electrode was produced in the same manner as the positive electrode A, and was designated as a positive electrode B.
−Ｆ記正極Ａ及びＢを夫々所定彩状に切断し、公称容量
１．３ＡＨのニッケルーカドミウム電池に用いる正極を
作製し、この正極を２ Ｃ（２，６Ａ）の電流で３００
？’ｏの過充電を行なった後、活物質の結晶構造をＸ線
回折法により同定した。第１図はこの結果を示す図面で
あり、この図面より、正極Ａはγ−Ｎ ｉ ＯＯＨの生
成がほとんど見られず、正極Ｂに比べて、γ−Ｎ ｉ
ＯＯＨの抑制効果があることがノっかる。- Cut the positive electrodes A and B in the specified color to prepare a positive electrode for use in a nickel-cadmium battery with a nominal capacity of 1.3 AH.
? After overcharging with 'o, the crystal structure of the active material was identified by X-ray diffraction. FIG. 1 is a drawing showing this result, and from this drawing, the positive electrode A shows almost no formation of γ-N i OOH, and compared to the positive electrode B, γ-N i
It is known that it has a suppressive effect on OOH.
次に、上記切断後の正極Ａ及びＢを用い、非焼結式カド
ミウム負極と組み合わせることにより、公称容量１．３
ＡＨのニッケルーカドミウム電池を夫々・１個作製し、
用いた正極に符号を対応させて電池Ａ及びＢとした。第
２図は、これらの電池のサイクル特性を示す図面である
。サイクル条件は、寿命加速条件とし、１．２Ｃの電流
で６０分間充電した後、抵抗を接続してＩＣ相当の電流
で２時間放電し、完全放電するようにした。サイクル試
験は、電池Ａ及びＢとも夫々４個ずつ行ない、第２図で
はこの結果を平均値で表示している。また、容量測定は
、放電電圧が１．ＯＶを切った時点の放電持続時間で算
出した。Next, by using the positive electrodes A and B after the above cutting and combining them with a non-sintered cadmium negative electrode, a nominal capacity of 1.3
Fabricate one AH nickel-cadmium battery,
Batteries A and B were designated by the codes corresponding to the positive electrodes used. FIG. 2 is a drawing showing the cycle characteristics of these batteries. The cycle conditions were life acceleration conditions, and after charging for 60 minutes with a current of 1.2C, a resistor was connected and discharged for 2 hours with a current equivalent to an IC, so that the battery was completely discharged. The cycle test was conducted on four batteries each for batteries A and B, and the results are shown as average values in FIG. In addition, when measuring the capacity, the discharge voltage is 1. It was calculated based on the discharge duration at the time when OV was turned off.
電池Ａ及びＢは、サイクル初期において電池容量がほぼ
同じであるが、電池Ａは良好なサイクル特性を示してい
るのに対し、電池Ｂは２００サイクル程度で大きく容量
が低トしている。サイクル試験終了後の電池Ｂを分解し
て調べてみると、正極が膨化してセパレータ中の電解液
が正極に移動しており、正、負極間の電解液量が減少し
ていることがわかった。Batteries A and B have almost the same battery capacity at the beginning of the cycle, but while battery A shows good cycle characteristics, battery B's capacity decreases significantly after about 200 cycles. When battery B was disassembled and examined after the cycle test, it was found that the positive electrode had expanded and the electrolyte in the separator had moved to the positive electrode, reducing the amount of electrolyte between the positive and negative electrodes. Ta.
これは、正極の基板中に添加したケイ素化合物によって
、充電時にγ−Ｎｉ００１１が生成することが抑制でき
、これによって、正極が膨化することにより発生するド
ライアウトが防止できたものと考えられる。This is thought to be because the silicon compound added to the positive electrode substrate suppressed the formation of γ-Ni0011 during charging, thereby preventing dry-out caused by swelling of the positive electrode.
尚、上記実施例では、焼結前の基板にケイ酸塩を噴霧し
たが、ケイ酸塩の添加方法はこれに限定されるものでは
なく、焼結前の基板をケイ酸塩溶液に浸漬しても良いし
、スラリー中にケイ酸塩をｆめ添加しておいても良い。In the above example, silicate was sprayed on the substrate before sintering, but the method of adding silicate is not limited to this, and the substrate before sintering was immersed in a silicate solution. Alternatively, a certain amount of silicate may be added to the slurry.
（ト）発明の効果
本発明の焼結式ニッケル正極の製造方法は、ニッケル粉
末を主体とし、ケイ酸もしくはケイ酸塩を添加した混合
物を焼結することを特徴とするため、ニッケル焼結体に
ケイ素化合物を添加することができ、これにより充電時
にニッケル活物質がγ−ＮｉＯＯＩｌに変化することを
抑制でき、充放電サイクル時の活物質の体積変化が少な
くなり、サイクルか命が向−１−する。(G) Effects of the Invention The method for producing a sintered nickel positive electrode of the present invention is characterized by sintering a mixture containing nickel powder as a main ingredient and adding silicic acid or silicate. By adding a silicon compound to the nickel active material, it is possible to suppress the change of the nickel active material into γ-NiOOIl during charging, and the volume change of the active material during charge/discharge cycles is reduced, which improves cycle life by -1 - to do.
第１図はＸ線回折図、第２図はサイクル特性図である。 手続補正書岨発） 平成 ２年 ７月 ２日 事件の表示 平成２年特許願第８９５００号 発明の名称 焼結式ニッケル正極の製造方法 補正をする者 事件との関係 特許出呻入 名 称 （１８８）三洋電機株式会社 FIG. 1 is an X-ray diffraction diagram, and FIG. 2 is a cycle characteristic diagram. Procedural amendments issued by Dian) July 2, 1990 Display of incidents 1990 Patent Application No. 89500 name of invention Manufacturing method of sintered nickel positive electrode person who makes corrections Relationship to the incident: Patent issue and entry Name (188) Sanyo Electric Co., Ltd.
Claims (1)
ケイ酸塩を添加した混合物を焼結して多孔性焼結基板を
作製した後、該基板に酸性ニッケル塩溶液への浸漬を伴
う活物質充填操作を行なうことを特徴とする焼結式ニッ
ケル正極の製造方法。(1) After producing a porous sintered substrate by sintering a mixture consisting mainly of nickel powder and glue with addition of silicic acid or silicate, the substrate is activated by immersion in an acidic nickel salt solution. A method for producing a sintered nickel positive electrode characterized by performing a substance filling operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089500A JPH03289050A (en) | 1990-04-03 | 1990-04-03 | Manufacture of sintered type nickel positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089500A JPH03289050A (en) | 1990-04-03 | 1990-04-03 | Manufacture of sintered type nickel positive electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03289050A true JPH03289050A (en) | 1991-12-19 |
Family
ID=13972486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2089500A Pending JPH03289050A (en) | 1990-04-03 | 1990-04-03 | Manufacture of sintered type nickel positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03289050A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012014895A1 (en) * | 2010-07-30 | 2012-02-02 | 三洋電機株式会社 | Sintered nickel cathode, method of manufacturing same, and alkaline storage battery employing the sintered nickel cathode |
-
1990
- 1990-04-03 JP JP2089500A patent/JPH03289050A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012014895A1 (en) * | 2010-07-30 | 2012-02-02 | 三洋電機株式会社 | Sintered nickel cathode, method of manufacturing same, and alkaline storage battery employing the sintered nickel cathode |
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