CN1279641C - Alkaline primary battery positive electrode material and preparation method of positive electrode thereof - Google Patents
Alkaline primary battery positive electrode material and preparation method of positive electrode thereof Download PDFInfo
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Abstract
Relates to a high-energy alkaline primary battery anode material and a preparation method of an anode thereof. The components are doped beta-NiOOH and electrolytic MnO 2 Mixing the mixture as active matter, and the auxiliary components are conductive agent and additive. Firstly preparing Zn and Co doped beta-Ni (OH) 2 The prepared doped beta-Ni (OH) 2 Adding into NaOH or KOH solution of 0.5-10 mol/L, then adding beta-Ni (OH) doped proportionally 2 Oxidizing excessive strong oxidant, filtering and washing to obtain doped beta-NiOOH, and mixing the doped beta-NiOOH with electrolytic MnO 2 Mixing the active substances as active substances, adding a conductive agent and an additive, uniformly mixing, rolling into sheets, granulating, and pressing a ring to obtain the battery anode. Good storage performance, large discharge capacity and further improved positive performance. And the product in solid form has good stability and price dominance. The self-discharge decomposition of the anode is prevented, and the intermittent discharge capability of the battery is improved.
Description
Technical Field
The invention relates to an alkaline battery, in particular to an alkaline primary battery anode material and a preparation method of an anode thereof.
Technical Field
The discharge capacity of the currently widely used alkaline manganese battery is greatly improved compared with that of the common zinc-manganese battery, but the discharge curve is uneven, the discharge capacity in a high-voltage section is low, and the like, so that the high-voltage and large-current discharge requirements of increasingly popular portable electronic equipment such as digital cameras, video cameras and the like cannot be well met. Lithium ion batteries and nickel-metal hydride batteries require chargers, are inconvenient to use and have high cost. For this purpose, it has been proposed to replace manganese dioxide (MnO) of the positive electrode of an alkaline manganese cell with beta-nickel oxyhydroxide (beta-NiOOH) 2 ) A novel high-energy alkaline primary battery is manufactured, so that high-voltage and high-current discharge can be realized. However, beta-NiOOH itself is easily decomposed and self-discharged, and has poor storage properties. CN99811767.6 discloses an alkaline battery, which adopts beta-NiOOH to partially replace MnO 2 The method integrates beta-NiOOH and MnO together to reduce self-decomposition of beta-NiOOH by adding additive as positive electrode material of the novel primary battery 2 The advantages of both properties are also effective in self-discharge decomposition of the positive electrode, but the instability of the beta-NiOOH itself is not reducedIs very effective. CN 01116672.X discloses a "positive electrode material and nickel-zinc battery", which is prepared by placing β -NiOOH in a pressure kettle containing alkali solution to make β -NiOOH contain alkaline cation to reduce its self-decomposition, but this method is complicated and difficult. CN02134736.0 discloses a "positive electrode material of alkaline battery and its preparation method", which improves the positive electrode material, synthesizes a beta-zinc oxyhydroxide crystal, can effectively reduce self-discharge decomposition of high-valence nickel, but actually has an oxidant better than the sodium hypochlorite used in the synthesis method in terms of performance and price. Moreover, none of these published patent applications has considered the problem of improving the proton conductivity of the β -NiOOH positive electrode to sufficiently increase the β -NiOOH discharge utilization rate.
Disclosure of Invention
The invention aims to provide a novel battery positive electrode material containing a doped beta-NiOOH active substance, which has high discharge capacity under the condition of high-voltage and large-current discharge and good storage performance, and a preparation method of a positive electrode thereof. The technical scheme of the invention is to prepare the doped beta-NiOOH with large discharge capacity and high stability, and the positive active substance adopts the doped beta-NiOOH and the electrolytic MnO 2 Mixed and used with additives that further improve the positive properties.
The alkaline primary battery positive electrode material comprises the following components in parts by mass:
1) Doping beta-NiOOH and electrolyzing MnO 2 Mixing the two as active substances, wherein the mass ratio of the two is 1: 0.25-4, and the total mass of the two is 100 parts;
2) 4-8 parts of a conductive agent;
3) 1-10 parts of additive by mass, wherein the additive is selected from La 2 O 3 ，AgO，ZrO 2 ，TiO 2 ，Be(OH) 2 ，Mg(OH) 2 ， Ca(OH) 2 ，Sr(OH) 2 ，Ba(OH) 2 And the like.
The conductive agent is selected from graphite, metal cobalt powder or metal nickel powder, etc.
The preparation method of the alkaline primary battery anode comprises the following steps:
1. preparation of doped beta-NiOOH:
1) Uniformly mixing 0.5-2 mol/L nickel salt solution, 0.5-2 mol/L zinc salt solution and 0.5-2 mol/L cobalt salt solution according to the proportion of Ni to Zn to Co =100 to (4-10) to (2-5), then carrying out parallel flow reaction with 1-10 mol/L NaOH or KOH solution and 12-14 mol/L ammonia water complexing agent under the stirring action, controlling the pH value of the solution to be 10-14, controlling the reaction temperature to be 40-65 ℃ and the reaction time to be 12-24 h to obtain Zn and Co doped beta-Ni (OH) 2 ；
2) The prepared doped beta-Ni (OH) 2 Doping 1Kg with beta-Ni (OH) 2 Adding the solution of 50-100 percent of LNaOH or KOH into 0.5-10 mol/L NaOH or KOH solution, and then adding beta-Ni (OH) doped in proportion 2 K in an amount 1.2 to 2 times greater than the amount of 2 S 2 O 8 Or KClO 3 Or KMnO 4 Oxidizing with equal-strength oxidant, controlling the temperature at 25-60 ℃, reacting for 12-24 h, filtering and washing to obtain doped beta-NiOOH;
2. doping beta-NiOOH with electrolytic MnO 2 Mixing the materials to be used as active substances, adding a conductive agent and an additive, uniformly mixing, rolling, granulating and pressing a ring to prepare a battery anode;
3. the contents of all components by mass ratio are as follows:
doped beta-NiOOH and electrolytic MnO 2 Mixing the active substances as 100 parts by mass, wherein the mass ratio of the active substances to the conductive agents is 1: 0.25-4, the conductive agents is 4-8 parts, and the additives are 1-10 parts and selected from La 2 O 3 ，AgO，ZrO 2 ， TiO 2 ，Be(OH) 2 ，Mg(OH) 2 ，Ca(OH) 2 ，Sr(OH) 2 ，Ba(OH) 2 And the like.
The preparation of the doped beta-NiOOH is based on the preparation of the beta-NiOOH, and the high-density beta-Ni (OH) doped with zinc and cobalt is prepared by an ammonia complex coprecipitation method 2 Then oxidizing the beta-Ni (OH) doped with zinc and cobalt by chemical oxidation 2 Thus obtaining the doped beta-NiOOH. The doping of zinc and cobalt in the beta-NiOOH can not only improve the oxygen evolution decomposition potential of the beta-NiOOH and prevent the self-discharge decomposition of the beta-NiOOH in the battery, but also improve the proton conductivity and electron conductivity of the beta-NiOOH by eutectic cobalt. beta-NiOOH in the positive electrode generates Ni (OH) with poor conductivity after discharging on a conductive agent such as graphite 2 Thereby isolating a portion of the undischarged β -NiOOH from the conductive agent and preventing further discharge. However, eutectic cobalt can convert encapsulated and isolated beta-NiOOH into Ni (OH) 2 Effectively performing proton diffusion to continue discharging, and fully utilizing the beta-NiOOH of the anode. Doping beta-Ni (OH) in chemical oxidation 2 The oxidizing agent is preferably potassium persulfate (K) 2 S 2 O 8 )，K 2 S 2 O 8 Compared with sodium hypochlorite used in the above patent applications, the sodium hypochlorite has strong oxidizability, good stability of the product existing in a solid form and high price.
Doping beta-NiOOH and electrolyzing MnO on positive electrode 2 The active substances are mixed to combine the advantages of the two. MnO (MnO) 2 Low cost, self-recovery in alkaline solution, strong intermittent discharge capability, and self-oxygen decomposition of beta-NiOOH to release oxygen capable of decomposing MnO 2 Reoxidizing the discharge product MnOOH to MnO 2 . The use of the mixed active material in this way not only prevents the self-discharge decomposition of the positive electrode, but also contributes to the improvement of the intermittent discharge capability of the battery (as is typical of digital cameras).
The positive electrode can adopt graphite, metal cobalt powder or metal nickel powder and the like as conductive agents, and TiO is added 2 、Ba(OH) 2 And the additives further improve the performance of the positive electrode.
The following is the reaction formula principle for preparing beta-NiOOH and discharging the battery.
Preparation reaction of NiOOH:
and (3) battery positive electrode reaction:
self-decomposition reaction of NiOOH:
oxidation reaction of MnOOH:
the specific implementation mode is as follows:
example 1
Preparation of doped beta-NiOOH:
uniformly mixing 0.5mol/L nickel salt solution, 2mol/L zinc salt solution and 1.5mol/L cobalt salt solution according to the proportion of Ni to Zn to Co =100 to 4, then carrying out cocurrent flow reaction with 5mol/L NaOH solution and 14mol/L ammonia water complexing agent under the stirring action, controlling the pH value of the solution to be 10, the reaction temperature to be 55 ℃, and the reaction time to be 18h, thus obtaining Zn and Co doped beta-Ni (OH) 2 。
The prepared doped beta-Ni (OH) 2 Dope beta-Ni (OH) with 1Kg 2 Adding 50 portions of LNaOH solution into 4mol/L NaOH solution, and then adding beta-Ni (OH) doped in proportion 2 1.5 times more amount of K 2 S 2 O 8 Strong oxidant is used for oxidation, the temperature is controlled to be 50 ℃, and the doped beta-NiOOH is obtained after reaction for 12h and filtration and washing.
Doping beta-NiOOH with electrolytic MnO 2 Mixing as active substance, adding conductive agent graphite and additive TiO 2 Mixing evenly, rolling, granulating and pressing a ring to prepare the battery anode.
The contents of all components by mass ratio are as follows: doping beta-NiOOH and electrolyzing MnO 2 The active substance is mixed, the mass of the active substance and the additive is 100 parts, the proportion of the active substance and the additive is 1: 1, the conductive agent is 5 parts, and the additive is 3 parts.
A battery is manufactured on an alkaline manganese battery production line by taking 40% concentrated KOH as electrolyte and zinc powder as a negative electrode. Of course, the active material can also be filled into the foamed nickel, rolled, cut and wound to form the battery.
Example 2
Preparation of doped beta-NiOOH:
uniformly mixing 1mol/L nickel salt solution, 0.5mol/L zinc salt solution and 0.5mol/L cobalt salt solution according to the proportion of Ni to Zn to Co =100 to 6 to 3, then carrying out cocurrent flow reaction with 10mol/L KOH solution and 13mol/L ammonia water complexing agent under the stirring action, controlling the pH value of the solution to be 14, the reaction temperature to be 40 ℃, and the reaction time to be 24h to obtain Zn and Co doped beta-Ni (OH) 2 。
The prepared doped beta-Ni (OH) 2 Doping 1Kg with beta-Ni (OH) 2 Adding 100 portions of NaOH solution into 0.5mol/L solution, then adding beta-Ni (OH) doped proportionally 2 1.2 times more KClO 3 Strong oxidant is used for oxidation, the temperature is controlled at 60 ℃, the reaction lasts for 18 hours, and then the mixture is filtered and washedThus obtaining the doped beta-NiOOH.
Doping beta-NiOOH and electrolyzing MnO 2 Mixing as active substance, adding metal cobalt powder as conductive agent and Ba (OH) as additive 2 Mixing evenly, rolling, granulating and pressing a ring to prepare the battery anode.
The contents of all components by mass ratio are as follows: doping beta-NiOOH and electrolyzing MnO 2 Mixing the active substances to obtain 100 parts of the active substances, wherein the mass ratio of the active substances to the active substances is 1: 2, the conductive agent is 8 parts, and the additive is 6 parts.
A battery is manufactured on an alkaline manganese battery production line by taking 40% concentrated KOH as electrolyte and zinc powder as a negative electrode. Of course, the active material can also be filled into the foamed nickel, rolled, cut and wound to form the battery.
Example 3
Preparation of doped beta-NiOOH:
uniformly mixing 1.5mol/L nickel salt solution, 1.5mol/L zinc salt solution and 1mol/L cobalt salt solution according to the proportion of Ni to Zn to Co =100 to 8 to 5, then carrying out cocurrent flow reaction with 1mol/L NaOH solution and 12mol/L ammonia water complexing agent under the stirring action, controlling the pH value of the solution to be 12, the reaction temperature to be 65 ℃, and the reaction time to be 12h to obtain Zn and Co doped beta-Ni (OH) 2 。
The prepared doped beta-Ni (OH) 2 Doping 1Kg with beta-Ni (OH) 2 Adding 70LKOH solution into 10mol/L KOH solution, and adding beta-Ni (OH) doped in proportion 2 KMnO in an amount 1.6 times more 4 Strong oxidant is used for oxidation, the temperature is controlled to be 25 ℃, and the doped beta-NiOOH is obtained after 20 hours of reaction, filtration and washing.
Doping beta-NiOOH and electrolyzing MnO 2 Mixing as active substance, adding metallic nickel powder as conductive agent and La as additive 2 O 3 Mixing uniformly, rolling, granulating and pressing a ring to prepare the battery anode.
Each component is based on the massThe content of the weight ratio is as follows: doping beta-NiOOH and electrolyzing MnO 2 The active substance is mixed, the mass ratio of the active substance to the conductive substance is 1: 0.25, the conductive agent is 6 parts, and the additive is 10 parts.
A battery is manufactured on an alkaline manganese battery production line by taking 40% concentrated KOH as electrolyte and zinc powder as a negative electrode. Of course, the active material can also be filled into the foamed nickel, rolled, cut and wound to form the battery.
Example 4
Preparation of doped beta-NiOOH:
uniformly mixing 2mol/L nickel salt solution, 1mol/L zinc salt solution and 2mol/L cobalt salt solution according to the proportion of Ni to Zn to Co =100 to 10 to 2, then carrying out parallel flow reaction with 3mol/L NaOH solution and 13mol/L ammonia water complexing agent under the stirring action, controlling the pH value of the solution to be 13, the reaction temperature to be 50 ℃, and the reaction time to be 12h to obtain Zn and Co doped beta-Ni (OH) 2 。
The prepared doped beta-Ni (OH) 2 Doping 1Kg with beta-Ni (OH) 2 80 percent of LNaOH solution is added into 7mol/L NaOH solution, and then beta-Ni (OH) is added in proportion 2 K in an amount 2 times greater 2 S 2 O 8 Oxidizing with strong oxidant at 40 deg.c for 24 hr, filtering and washing to obtain doped beta-NiOOH.
Doping beta-NiOOH with electrolytic MnO 2 Mixing the active substances, adding graphite as conductive agent and ZrO as additive 2 Mixing evenly, rolling, granulating and pressing a ring to prepare the battery anode.
The contents of all components by mass ratio are as follows: doping beta-NiOOH and electrolyzing MnO 2 Mixing the active substances to obtain 100 parts of the active substances, wherein the mass ratio of the active substances to the active substances is 1: 4, the conductive agent is 4 parts, and the additive is 1 part.
A battery is manufactured on an alkaline manganese battery production line by taking 40% concentrated KOH as electrolyte and zinc powder as a negative electrode. Of course, the active material can also be filled into the foamed nickel, rolled, cut and wound to form the battery.
Example 5
Preparation of undoped NiOOH: 2mol/L of NiSO 4 The solution is reacted with 5mol/L NaOH solution and 13mol/L ammonia water complexing agent in a cocurrent way under the stirring action. The pH value of the solution is controlled to be 12 +/-0.5, and the reaction temperature is controlled to be 55 ℃. Reacting for 12h to obtain undoped Ni (OH) 2 . 2Kg of Ni (OH) doped alloy 2 Adding 100L of 1mol/L NaOH while stirring, adding 8Kg of K after stirring uniformly 2 S 2 O 8 And oxidizing at 40 deg.c for 12 hr to obtain doped NiOOH.
Preparation of Zn-only doped beta-NiOOH: 2mol/L of NiSO 4 Solution and 2mol/L ZnSO 4 The solution is evenly mixed according to the proportion of Ni to Zn =100 to 6, and then the solution is reacted with 5mol/L NaOH solution and 13mol/L ammonia water complexing agent in a cocurrent flow manner under the stirring action, the pH value of the solution is controlled to be 12 +/-0.5, and the reaction temperature is 55 ℃. Reacting for 12h to obtain Zn-doped beta-Ni (OH) 2 . 2Kg of Zn-doped beta-Ni (OH) 2 Adding 100L of 1mol/L NaOH while stirring, adding 8Kg of K after stirring uniformly 2 S 2 O 8 Oxidizing at 40 deg.c for 12 hr to obtain Zn doped productNiOOH。
Preparation of Zn and Co doped beta-NiOOH: 2mol/L of NiSO 4 Solution and 2mol/L ZnSO 4 Solution, 2mol/L CoSO 4 Uniformly mixing the solution Ni, zn and Co = 100: 6: 3, and then carrying out cocurrent reaction on the solution, 5mol/L NaOH solution and 13mol/L ammonia water complexing agent under the stirring action to control the pH value of the solution to be 12 +/-0.5 and the reaction temperature to be 55 ℃. Obtaining Zn and Co doped beta-Ni (OH) 2 . 2Kg of doped beta-Ni (OH) 2 Adding 100L of 1mol/L NaOH while stirring, adding 8Kg of K after stirring uniformly 2 S 2 O 8 Oxidizing at 40 deg.C for 12 hr to obtainObtaining NiOOH doped with Zn and Co.
Example 6
Several examples of preparing positive electrodes are given below:
1#, mixing undoped beta-NiOOH and electrolytic MnO 2 Mixing the active material and graphite (accounting for 5% of the mass of the anode) according to the mass ratio of 4: 6, uniformly mixing, rolling, granulating and pressing a ring to obtain the 5# cylindrical battery anode ring. And (3) preparing a 5# battery on an alkaline manganese battery production line by using 40% concentrated KOH as electrolyte and zinc paste as a negative electrode. One batch is placed for 12h and then tested for new electrical property by a 1.8 omega pulse and 1000mA continuous discharge, and the other batch is stored at the high temperature of 70 ℃ for 20 days and then tested for discharge property after high-temperature storage by a 1.8 omega pulse and 1000mA continuous discharge. This was used as a control.
2#, beta-NiOOH doped with Zn only and electrolytic MnO 2 Mixing the active material and graphite (accounting for 5% of the mass of the anode) according to the mass ratio of 4: 6, uniformly mixing, rolling, granulating and pressing a ring to obtain the 5# cylindrical battery anode ring. And (3) preparing a 5# battery on an alkaline manganese battery production line by using 40% concentrated KOH as electrolyte and zinc paste as a negative electrode. One batch is placed for 12 hours and then is tested for new electrical property by continuous discharge of 1.8 omega pulse and 1000mA, and the other batch is stored for 20 days at the high temperature of 70 ℃ and then is tested for discharge property after high-temperature storage by continuous discharge of 1.8 omega pulse and 1000 mA. This was used as a control.
3#, the Zn and Co doped beta-NiOOH and electrolytic MnO 2 Mixing the active material and graphite (accounting for 5% of the mass of the anode) according to the mass ratio of 4: 6, uniformly mixing, rolling, granulating and pressing a ring to obtain the 5# cylindrical battery anode ring. And (3) preparing a 5# battery on an alkaline manganese battery production line by using 40% concentrated KOH as electrolyte and zinc paste as a negative electrode. One batch is placed for 12h and then tested for new electrical property by continuous discharge of 1.8 omega pulse and 1000mA, and the other batch is stored at the high temperature of 70 ℃ for 20 days and then tested for discharge property after high-temperature storage by continuous discharge of 1.8 omega pulse and 1000 mA.
4#, mixing Zn and Co doped beta-NiOOH with electrolytic MnO 2 Mixing the raw materials according to the mass ratio of 4: 6 to be used as an active substance, taking graphite (accounting for 5 percent of the mass of the anode) as a conductive agent, and ZrO 2 (accounting for 3 percent of the mass of the anode) is used as an additive, and the 5# cylindrical battery anode ring is prepared by uniformly mixing, flaking, granulating and pressing a ring. And (3) preparing a 5# battery on an alkaline manganese battery production line by using 40% concentrated KOH as electrolyte and zinc paste as a negative electrode. One batch is placed for 12h and then tested for new electrical property by continuous discharge of 1.8 omega pulse and 1000mA, and the other batch is stored at the high temperature of 70 ℃ for 20 days and then tested for discharge property after high-temperature storage by continuous discharge of 1.8 omega pulse and 1000 mA.
And 5#, replacing the additive in the 4# with AgO, manufacturing the battery according to the same method of the 4# and performing the same test.6# and 4# by changing the additive into La 2 O 3 Batteries were made in the same manner as # 4 and the same tests were performed. 7# and 4# the additive is changed into Ba (OH) 2 Batteries were made in the same manner as in # 4 and the same tests were performed.
Table 1 average results of the tests
| Battery with a battery cell Number of | Discharging after standing for 12h | Discharging after 20 days of storage at 70 DEG C | ||||
| Open pressure (V) | 1.8 omega pulse amplifier When electricity reaches 1.2V Number of arrivals | 1000mA continuous discharge To 1.0V Duration (min) | Open pressure (V) | 1.8 omega pulse Discharge to 1.2V Number of arrival times | 1000mA continuous discharge To 1.0V Duration (min) | |
| 1# | 1.739 | 220 | 46.9 | 1.698 | 106 | 25.2 |
| 2# | 1.721 | 217 | 45.6 | 1.703 | 186 | 34.5 |
| 3# | 1.729 | 253 | 55.5 | 1.700 | 211 | 42.9 |
| 4# | 1.722 | 250 | 56.1 | 1.701 | 232 | 48.1 |
| 5# | 1.718 | 241 | 58.0 | 1.708 | 225 | 47.6 |
| 6# | 1.730 | 256 | 57.5 | 1.702 | 229 | 49.5 |
| 7# | 1.725 | 257 | 58.9 | 1.705 | 237 | 50.7 |
From the test results in Table 1, it can be seen that Zn and Co doped beta-NiOOH and MnO are contained 2 The alkaline primary battery mixed as the anode has the performance of intermittent discharge or continuous discharge under the condition of high current and high voltage discharge which is higher than that of undoped beta-NiOOH or beta-NiOOH and MnO which are only doped with Zn 2 The alkaline primary battery is much better, especially in high-temperature storage performance.
Claims (4)
1. The positive electrode material of the alkaline primary battery is characterized by comprising the following components in parts by mass:
1) Doping beta-NiOOH with electrolytic MnO 2 Mixing the two as active substances in a ratio of 1: 0.25-4, wherein the mass of the two is 100 partsThe doping elements in the mixed beta-NiOOH are Zn and Co, the amounts of the doping elements are 4-10% and 2-5% of the Ni content in the beta-NiOOH crystal lattice respectively, and the electrolytic MnO is 2 For preparing MnO by adopting electrolytic method 2 ；
2) 4-8 parts of a conductive agent by mass;
3) 1-10 parts of additive by mass, wherein the additive is selected from La 2 O 3 ，AgO，ZrO 2 ，TiO 2 ，Be(OH) 2 ，Mg(OH) 2 ， Ca(OH) 2 ，Sr(OH) 2 ，Ba(OH) 2 At least one of (1).
2. The positive electrode material for alkaline primary batteries according to claim 1, wherein said conductive agent is selected from the group consisting of graphite, metallic cobalt powder and metallic nickel powder.
3. The preparation method of the alkaline primary battery anode is characterized by comprising the following steps:
1) And preparing doped beta-NiOOH:
(1) Uniformly mixing 0.5-2 mol/L nickel salt solution, 0.5-2 mol/L zinc salt solution and 0.5-2 mol/L cobalt salt solution according to the proportion of Ni to Zn to Co = 100: 4-10: 2-5, then carrying out cocurrent flow reaction with 1-10 mol/L NaOH or KOH solution and 12-14 mol/L ammonia water complexing agent under the stirring action, controlling the pH value of the solution to be 10-14, the reaction temperature to be 40-65 ℃, and the reaction time to be 12-24 h, thus obtaining Zn and Co doped beta-Ni (OH) 2 ；
(2) The prepared doped beta-Ni (OH) 2 Dope beta-Ni (OH) with 1Kg 2 50-100 portions of NaOH or KOH solution is added into 0.5-10 mol/L of NaOH or KOH solution, and then beta-Ni (OH) doped with the mixture is added 2 K in an amount 1.2 to 2 times greater than the amount of 2 S 2 O 8 Or KClO 3 Or KMnO 4 Strong oxidant is used for oxidation, the temperature is controlled to be 25-60 ℃, and the reaction is carried outFiltering and washing the mixture after 12 to 24 hours to obtain doped beta-NiOOH;
2) Doping beta-NiOOH and electrolyzing MnO 2 Mixing the materials as active substances, adding a conductive agent and an additive, uniformly mixing, rolling, granulating and pressing a ring to prepare a battery anode;
3) The contents of the components by mass ratio are as follows:
doping beta-NiOOH and electrolyzing MnO 2 Mixing the active substances as 100 parts by mass, the ratio of the active substances to the conductive agent is 1: 0.25-4, the conductive agent is 4-8 parts, the additive is 1-10 parts, and the additive is selected from La 2 O 3 ，AgO，ZrO 2 ，TiO 2 ， Be(OH) 2 ，Mg(OH) 2 ，Ca(OH) 2 ，Sr(OH) 2 ，Ba(OH) 2 Wherein the doped elements in the doped beta-NiOOH are Zn and Co, the amounts of which are respectively 4% -10% and 2% -5% of the Ni content in the beta-NiOOH crystal lattice, and the electrolytic MnO is 2 For preparing MnO by electrolytic method 2 。
4. The method for producing a positive electrode for an alkaline primary battery according to claim 3, wherein said conductive agent is selected from the group consisting of graphite, metallic cobalt powder and metallic nickel powder.
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| CN101267047B (en) * | 2007-03-16 | 2010-10-06 | 深圳市力可兴电池有限公司 | Nickel-hydrogen rechargeable battery |
| US8048566B2 (en) * | 2008-02-07 | 2011-11-01 | Powergenix Systems, Inc. | Nickel hydroxide electrode for rechargeable batteries |
| CN102306763A (en) * | 2011-08-26 | 2012-01-04 | 浙江特源电池有限公司 | Cylindrical alkaline zinc-manganese battery positive electrode powder and preparation method thereof |
| US9337483B2 (en) | 2013-01-14 | 2016-05-10 | Powergenix Systems, Inc. | Pasted nickel hydroxide electrode and additives for rechargeable alkaline batteries |
| CN115312732A (en) * | 2022-08-31 | 2022-11-08 | 河南超力新能源有限公司 | Low-cost alkaline secondary battery positive electrode material and preparation method and application thereof |
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