CN1013434B - Method for producing chemical manganese dioxide for battery - Google Patents
Method for producing chemical manganese dioxide for batteryInfo
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- CN1013434B CN1013434B CN 88100201 CN88100201A CN1013434B CN 1013434 B CN1013434 B CN 1013434B CN 88100201 CN88100201 CN 88100201 CN 88100201 A CN88100201 A CN 88100201A CN 1013434 B CN1013434 B CN 1013434B
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Abstract
The present invention relates to a method for preparing chemical manganese dioxide for battery. Manganese dioxide prepared by oxidizing manganese salt by using chlorine as a chlorinating agent can be suitable for the requirement of the battery. The method comprises the following steps: in the process of preparing primary manganese dioxide, reaction is controlled at 82-95 ℃, and 95 g/L MgO is added as a pH regulator according to the addition amount of 2.0-4.0 g/h of manganese salt solution per liter. Then adopting the following steps: introducing hot high-pressure saturated steam for pressurizing treatment and sodium chlorate chemical method for secondary heavy treatment. Thereby further improving the performance of the chemical manganese dioxide product. The method is suitable for manufacturing the chemical manganese dioxide product for the battery by taking manganese ore, chlorine, sulfuric acid and hydrochloric acid as raw materials.
Description
The present invention relates to a method for producing manganese dioxide by using manganese ore as raw material, in particular it is suitable for producing chemical manganese dioxide for battery.
Electrochemically active manganese dioxide, such as natural battery grade manganese dioxide, chemical Manganese Dioxide (CMD), electrolytic Manganese Dioxide (EMD), and the like, is widely used as a cathode active material in zinc-manganese batteries. Because natural battery grade manganese dioxide deposits are decreasing day by day, people adopt methods such as chemistry or electrolysis to prepare artificial active manganese dioxide-chemical manganese dioxide and electrolytic manganese dioxide. Chemical manganese dioxide has the advantage of price compared with electrolytic manganese dioxide, and can meet the requirements of batteries in performance, so that various manufacturing methods of chemical manganese dioxide are developed at home and abroad. The chemical method can be basically divided into: manganese carbonate pyrolysis, manganese nitrate decomposition, direct oxidation, and the like. The direct oxidation method is to select different oxidants to react manganese (Mn) 2+ ) Oxidation to manganese dioxide (Mn) 4+ ). U.S. Pat. No. 3,414,440 describes the direct oxidation of r-MnO with chlorine as an oxidant 2 In the method of (a) to (b),namely, selecting a manganese salt solution (MnSO) with the manganese content of 5 to 30 weight percent and no impurities basically 4 Or MnCl 2 ) In contrast to newly generated r-MnO 2 In the presence of seed crystal with the amount of 1.5-10.0 wt%, regulating the pH value to 0.5-3.0 with neutralizer, controlling the reaction temperature to 25-82 deg.c, introducing chlorine gas continuously to react, stopping the reaction before permanganate ion is generated, separating, washing and drying the precipitate to obtain chemical r-MnO 2 And (5) producing the product. The method for preparing the chemical manganese dioxide has simple process and is suitable for the condition of China. However, solid cells require that the tap density of the chemical manganese dioxide be greater than 1.6 g/cm 3 Otherwise, the total content of manganese dioxide in the battery can of a given capacity decreases, resulting in a decrease in the battery discharge capacity (i.e., a decrease in discharge time). The chemical manganese dioxide obtained by the method of the patent has low tap density and cannot meet the requirements of solid batteries.
Therefore, the present invention is directed to a method for manufacturing chemical manganese dioxide for batteries using manganese ore as a raw material. The method improves the existing method for preparing chemical manganese dioxide by directly oxidizing by using chlorine as an oxidizing agent by utilizing the characteristics of rich manganese ore resources and easy sources of sulfuric acid, hydrochloric acid and chlorine in China, and performs weight treatment on the newly prepared chemical manganese dioxide on the basis to ensure that the newly prepared chemical manganese dioxide meets the requirements of manganese dioxide for batteries.
The invention is composed of: manganese salt (MnSO) prepared by using manganese ore as raw material 4 Or MnCl 2 ) Purifying solution, directly oxidizing the manganese salt purified solution by adopting chlorine as an oxidant to prepare primary manganese dioxide, carrying out weight treatment on the primary manganese dioxide to prepare a chemical manganese dioxide product for the battery, recycling waste liquid, and carrying out four procedures.
The results from the experiments show that: the larger the crystallinity value D of the manganese dioxide crystal grains is, the better the discharge performance is, the larger the most probable pore diameter of the manganese dioxide crystal grains is, the better the discharge performance is, and the larger the main particle size distribution of the manganese dioxide crystal grains is, the better the tap density is. The key to determining these characteristics of the manganese dioxide grains is the second and third steps. The invention is different from the prior art in the following points:
one is as follows: in the second step, because chlorine gas is introduced into the manganese salt solution, a chemical reaction between gas and liquid occurs, and new manganese dioxide crystal grains are generated in the presence of seed crystals, so that the newly generated manganese dioxide has better characteristics, the process conditions in the crystallization process play an important role, and proper PH regulators and the addition amounts of the PH regulators are selected, and the reaction temperature (solution temperature) and the chlorine gas dosage are controlled, so that the reaction temperature is as follows: mgO is selected as the PH regulator at 82-95 ℃, and 95 g/L MgO slurry is added according to the addition of 2.0-4.0 g/h of manganese salt purification solution per liter, and the using amount of chlorine is 100-150 ml/min. Thus, the primary manganese dioxide with large crystallinity value D, large most probable pore diameter and main particle size distribution of 300-400 meshes can be obtained, and the foundation is laid for the third procedure.
And the second step is as follows: in the third step of the reforming treatment, the electrochemical activity is further improved by reducing the pores between the manganese dioxide particles to increase the tap density, in addition to maintaining the above-mentioned original physicochemical properties of the primary manganese dioxide, and this is the purpose of the reforming treatment. Here, theThe method comprises the following steps: first, primary manganese dioxide is pressurized to a first weight-conversion treatment using saturated hot high-pressure steam, and then the pressurized manganese dioxide is chemically subjected to a second weight-conversion treatment using sodium chlorate. The water vapor pressurization can ensure that manganese dioxide crystal grains at each part are uniformly pressurized, thereby avoiding the crystal grains from being crushed, reducing the pores among the particles and being beneficial to the mass production of manganese dioxide. In addition, the chemical activation is more important, because a small amount of water enters MnO after being pressurized by water vapor 2 Inside the crystal lattice to form MnO 2 Bound Water (coded Water), which is precisely r-MnO 2 Inherent in the characteristics of better discharge performance. Referring to the attached figure, the manganese dioxide crystal grains after the steam pressure treatment are tested by Fourier transform infrared spectroscopy and are found to have 3000-3600 cm -1 The characteristic of the O-H bond stretching vibrationAnd (4) peak. The existence of the characteristic peak indicates that partial water is combined in the crystal to separate out protons, and O-H bonds exist, so that the electrochemical activity is enhanced due to the existence of the protons. In addition, a certain amount of water molecules are adsorbed on the crystal surface, especially on the crystal surface O - 2 Water adsorption in place, easy to form hydrogen bond, and O 2- Slightly displaced and slightly activated, and the hydrogen bonds are easily broken during the second heavy treatment, so that newly formed Mn 4+ Instead, not only the newly formed MnO 2 Enter the original MnO 2 The inner surface of the pores of the particles and also a portion of newly formed MnO 2 Become original MnO 2 The grain growth reaches the purpose of secondary weight.
The four procedures of the invention are detailed as follows:
1. preparing a manganese salt purification solution:
the manganese ore is selected from manganese oxide ore or manganese carbonate ore, and manganese sulfate or manganese chloride purified solution is prepared according to the following method according to the requirement:
the method I comprises the following steps: the manganese sulfate purification liquid is prepared. Drying and crushing manganese ore to 100-160 meshes (if manganese oxide ore is roasted, reduced and then crushed) manganese ore powder for later use. Taking an industrial sulfuric acid aqueous solution with the concentration of 10-15%, stirring, heating to 70-80 ℃, adding manganese ore powder for reaction in batches, and respectively adding an oxidant MnO when the reaction is finished 2 Neutralizer MnCO 3 BaS, etc., then filtering and precipitating, removing filter residue and obtaining the manganese-containing content of 20.0-28.0 g/lThe purified manganese sulfate solution is ready for use.
And a method II: preparing the manganese chloride purifying liquid. Drying and crushing the manganese ore to 100-120 meshes (the manganese oxide ore treatment is the same as the above) of manganese ore powder for later use. Taking 10-15% industrial hydrochloric acid water solution, and obtaining the manganese chloride purifying solution with 20.0-28.0 g liter of manganese content for later use by the same steps as the method I.
2. Preparing primary manganese dioxide:
the manganese salt purified solution obtained in the above is sent into an oxidation reaction container, and then saturated chlorine gas as an oxidant is introduced for oxidation reaction, and the process conditions are controlled as follows:
1. manganese salt solution: manganese sulfate or manganese chloride purified liquid with manganese content of 20.0-28.0 g/L.
2. The amount of chlorine gas used is as follows: is fed in an amount of 100-150 ml/min, and when the reaction is carried out until Mn in the solution 2+ When the content of (b) is less than 0.01N, the introduction of chlorine gas is stopped, and the reaction is stopped.
3. pH value: 1 to 2.
4. PH adjuster (i.e., neutralizer): selecting MgO or Mg (OH) 2 Adding 2.0-4.0 g/h of MgO mud into each liter of manganese salt purifying solution. If Mg (OH) is adopted 2 Mg (OH) can be converted according to the amount of MgO 2 The amount of (c) added.
5. Seed crystal: using gamma-MnO of 200 mesh size 2 The dosage of the manganese dioxide is 8-15% of the weight of the primary manganese dioxide dry product generated by the reaction.
6. Reaction temperature: 82 to 95 ℃.
7. Stirring: stirring is continued.
8. Reaction termination time: stopping the introduction of the chlorine gas is the termination of the reaction.
Filtering the reaction product, washing the filtrate with water until the pH value is 6.5-7, and heating to 80-100 ℃ for drying to obtain the primary manganese dioxide product. The obtained filtrate and washing water are sent to recovery treatment as waste liquid.
3. Carrying out weight treatment on the primary manganese dioxide to prepare a chemical manganese dioxide product for the battery:
carrying out primary and secondary heavy processing in two steps, which comprises the following steps:
1. putting the primary manganese dioxide product into a high-pressure sealed container, and then introducing the manganese dioxide product into the container at the temperature of between 150 and 250 ℃ and under the pressure of between 2 and 6 kilograms per centimeter 2 Saturated water vapor and maintaining the corresponding pressureThe force is reduced to normal pressure for 1 to 6 hours, and then the manganese dioxide is taken out, washed by water and dried at the temperature of 80 ℃.
2. The manganese dioxide treated (pressurized) above was fed into a reaction vessel and then mixed in the following weight ratio:
MnO 2 ∶MnSO 4 = 1: 0.19-0.20 (optimally 0.195),
MnO 2 ∶H 2 SO 4 (1.84) = 1: 0.05-0.10 (optimally 0.09).
MnO 2 ∶NaClO 3 = 1: 0.10-0.15 (optimally 0.138),
firstly, manganese sulfate solution and sulfuric acid (1.84) solution are added into a container, stirred and added with proper amount of water to lead MnSO in the solution 4 1.46M, heated to 95 ℃ and added with NaClO in portions while stirring 3 And after the reaction is finished, filtering, washing the precipitated product with hot water until the pH value is 6-6.5, and drying to obtain the chemical manganese dioxide product for the battery.
4. And (3) waste liquid recovery treatment:
heating, evaporating and concentrating the waste liquid obtained by preparing primary manganese dioxide until the Mg content in the solution is 0.8-1.5 mol/liter, adding ammonia water or slaked lime and controlling the conditions to ensure that Mg (OH) 2 Deposition, deposited Mg (OH) 2 Filtered, dried and sent to be used as a PH regulator for recycling. Then, ammonia water is added into the residual solution, so that ammonium sulfate and ammonium chloride can be crystallized and separated out during heating and evaporation, and the ammonium sulfate and the ammonium chloride are recovered.
The invention adopts the method of directly oxidizing the chlorine as the oxidant to prepare the primary manganese dioxide and then carrying out secondary weight treatment by using the water vapor and the sodium chlorate, so that the method realizes the preparation of the chemical manganese dioxide product which can be used for the battery by using the manganese ore as the raw material and achieves the expected target. And the method is completely suitable for the conditions of China due to simple process, easy operation, waste liquid recovery, low cost and wide raw material sources. The chemical manganese dioxide product of the invention has the characteristics of large crystallinity value D, large pore diameter of the largest possible number, main particle size distribution of 300-400 meshes, high tap density and the like. All main indexes completely reach or exceed the industrial standards of electrolytic manganese dioxide of national Ministry of chemical industry, HGI-710-69, ministry of light industry, QB845-85, ZBG13001-86, JISK1467-1984, and the like. It is especially suitable for cathode active material of alkaline or ammonium cell. The performance of the product reaches the high-quality product of chemical manganese dioxide- "Faradizer M" for the battery produced by Sedema of European manganese products company Belgium.
The performance is compared as follows:
1. particle size distribution (see table 1 for results of sieve tests using standard sieves).
2. Tap density, crystallinity value D, mode pore size, and results are shown in table 2. Table 2 illustrates: the tap density is tested by a tapping method, the most probable aperture is tested by an ST-03 surface aperture determinator, and the crystallinity value D is obtained by subtracting the background (taking quartz as a reference substance) from the obtained data after an X-ray diffraction test according to the following steps:
scherer equation D = 36.563/(β y2. Cose)
(β y2 is the half width of the peak and is the Bragg angle) was calculated as the value of the crystallinity D.
3. Making a solid battery discharge condition:
(1) To produce R 6 Battery 5 Ω discharge case:
the formula of the battery cell powder is as follows: the manganese powder accounts for 88 percent of the electric core powder (wherein the chemical manganese dioxide product powder accounts for 70 percent, the natural manganese powder accounts for 30 percent), the acetylene black accounts for 12 percent of the electric core powder, and NH accounting for 16 percent of the solid powder (the manganese powder and the acetylene black) is additionally added 4 Cl, internal electrolyte adopts 17.5B' e +340 g NH 4 And (4) Cl. All calculated by weight.
5 Ω continuous and 5 Ω intermittent (5 min/day) to 0.9 v, the results are shown in table 3. The cells were incubated at 75 Ω (4 hr/day) to 0.9V, and the results are shown in Table 4.
The attached drawings are as follows: fourier transform infrared spectrum graphs of the chemical manganese dioxide sample and the Faradizer M sample are provided. Wherein curve "(1)" is a curve of a sample of the chemical manganese dioxide of the present invention and curve "(2)" is a curve of a sample of "Faradizer M".
Example (b):
example 1: 30 liters of manganese sulfate solution with the concentration of 70 grams/liter is prepared from Hunan Tan carbonic acid ore according to the method I in the first manganese salt purified solution preparation process. The solution was poured into a 60 liter oxidation tank, and saturated chlorine gas was introduced into the solution at a rate of 130 ml/min, and then γ -MnO was added 2 120 g of seed crystal, adding 95 g/l of MgO slurry according to the amount of 68.4 g/h (1.14 g/min), adjusting the pH to 1.8, controlling the total amount of the MgO slurry to 14.4 l, continuously stirring, controlling the reaction temperature to be between 90 and 92 ℃, after 20 hours of reaction, filtering, washing with water, and drying to obtain 1212 g of dry primary manganese dioxide. 500 g of the obtained primary manganese dioxide was taken out and charged into a 1L high-pressure vessel, and after sealing, the vessel was charged with 200 ℃ and 4 kg/cm pressure 2 Reducing the pressure to normal pressure after keeping the corresponding pressure for 4 hours, taking out, washing, drying, feeding into a 1L three-neck flask, respectively adding 291 ml of 2.23M manganese sulfate solution and 45 g of sulfuric acid (1.84) into the flask, stirring uniformly, standing for 8 hours, and adding 414 ml of water to ensure that MnSO in the solution is added 4 Heating to 95 ℃ at a concentration of 1.46M, adding 69 g of sodium chlorate in portions within 20-30 minutes under the condition of continuously stirring, continuing to react for 90 minutes, filtering, washing with water until the pH value is 6-6.5, and drying at 105-115 ℃ to obtain 536 g of chemical manganese dioxide finished product for the battery. The remaining waste liquid is treated by a conventional method in the step of "waste liquid recovery treatment" to recover Mg (OH) 2 (for recycle), (NH) 4 ） 2 SO 4 、NH 4 Cl, and the like.
Preparing the chemical manganese dioxide finished product for the battery into R 20 Paperboard battery (manganese-carbon ratio of 88: 1)12, plus 16% 4 Cl, the total weight of the battery cell is 58 g, the water content is 20 +/-1 percent), and the conditions of continuous discharging of 5 omega and discharging to 0.9 volt between 5 omega are as follows:
open circuit voltage: 1.77 volts, load voltage: the voltage of the power supply is 1.61V,
short-circuit current: 7.4 amperes, continuous storage time: the rate of the reaction is 590 minutes,
intermittent discharge time: 1564 min.
Example 2: manganese oxide ore in Fujian city is roasted and reduced to prepare 30 liters of manganese chloride purified solution with the concentration of 0.46M according to the method II in the first preparation process of manganese salt purified solution. The solution was poured into a 60 liter oxidation tank, saturated chlorine gas was introduced into the solution at a rate of 150 ml/min, and γ -MnO was added 2 120 g of seed crystal, and 83.64 g/h (1.390 g/min) of MgO slurry with the volume of 95 g/l is added, the PH is adjusted to be 1.8 to 1.9, the total consumption of the MgO slurry is 18.93 l, the mixture is continuously stirred, the reaction temperature is controlled to be 85 to 90 ℃, the reaction is finished after 21.5 h, and 1170 g of dry primary manganese dioxide is obtained by filtering, water washing and drying. 500 g of the obtained primary manganese dioxide was taken out and charged into a 1L high-pressure vessel, and after sealing, the vessel was charged with 200 ℃ and a pressure of 5 kg/cm 2 Reducing the pressure to normal pressure after the saturated water vapor is kept at the corresponding pressure for 3 hours, taking out, washing, drying, feeding into a 1L three-neck flask, respectively adding 705 ml of 1.46M manganese sulfate solution and 45 g of sulfuric acid (1.84) into the flask, standing for 8 hours after uniformly stirring, heating to 95 ℃, and carrying out the rest according to the 'example 1' to obtain 530 g of a chemical manganese dioxide finished product for the battery. The remaining waste liquid is treated by a conventional method in the step of "waste liquid recovery treatment" to recover Mg (OH) 2 、NH 4 Cl, and the like.
The prepared finished product of the chemical manganese dioxide for the battery is subjected to laboratory discharge and solid battery discharge tests, and the test conditions are as follows:
(1) Discharge in the laboratory:
using 25Cm 3 Capacitive organic glass discharge device, obtained as in example 20.1 g of chemical manganese dioxide powder, 2 g of graphite powder and 0.7 ml of 9MKOH electrolyte are fully stirred and mixed, and then the mixture is pressurized to 40 kg/cm 2 And the pressure is kept for 2 minutes, 16 ml of 9MKOH electrolyte is added, the mixture is placed overnight, and 5 milliampere constant current continuous discharge is carried out at room temperature (20-25 ℃) until the voltage reaches 0.9V: open circuit voltage: 1.49 volts, load voltage: 1.45 volts, continuous discharge time: 320 minutes.
(2) To form R 6 Physical cell (ammonium type) case:
the chemical manganese dioxide powder of example 2, 88%, acetylene black 12%, plus NH 4 Cl16%, internal electrolyte liquid 17.5Be' +340 g NH 4 And Cl, adopting 112 g of powder with the liquid adding amount of 51 ml, 20% of cell moisture and 7.2 g of cell weight. The conditions of continuous discharge of 5 omega and discharge between 5 omega to 0.9V are as follows: open circuit voltage: 1.66 volts, short circuit current: 3.1 ampere, load voltage: 1.40 volts, continuous discharge time: 60 minutes, time of rest: 155 minutes.
TABLE 2
Tap density crystallinity value, most probable pore size of sample
(g/cm) 3 ） D （121）
Faradizer.M 1.8 100 
18～20 
Is 41.3 percent
The product of the invention is 1.7 to 1.8 to 250 to 290
24～30 
Is 57.2 percent
TABLE 3
300 g of cell core water cell weighs 5 omega (continuous discharge) and 5 omega (intermittent discharge)
Sample powder with electrolyte amount parts (%) in grams (min)
(ml)
Inventive sample 120.2.8.2 43 190
Faradizer.M 120 21.7 8.2 45 176
TABLE 4
Sample 75 omega interval (minute)
4080 to 4130 samples of the present invention
Faradizer.M 3840～3920
Claims (3)
1. A process for preparing chemical manganese dioxide from manganese ore includes preparing the purified solution of manganese sulfate or manganese dichloride from manganese ore, and preparing the solution of manganese sulfate or manganese dichloride from MgO (or Mg (OH) 2 ) Introducing chlorine gas at 82-95 ℃ as a pH regulator to directly oxidize manganese salt solution to prepare primary manganese dioxide, and carrying out secondary weight treatment on the primary manganese dioxide, and is characterized in that:
and (3) an oxidation treatment process: manganese content of the manganese salt purification solution is 20.0-28.0 g/L, mgO content is 95 g/L, 2.0-4.0 g/h is added into each liter of manganese salt solution until pH value of the solution is 1-2, and saturated chlorine gas is introduced according to 100-150 ml/min until Mn in the solution 2+ Until the ion content is less than 0.01N,
and (3) heavy processing: the first time is to introduce the pressure of 2-6 kg/cm at the temperature of 150-250 DEG C 2 The manganese dioxide is pressurized for 2 to 6 hours by saturated water vapor, and the second time is chemical treatment by sodium chlorate.
2. According to claim 1The method for preparing chemical manganese dioxide is characterized in that the pressure of saturated steam can adopt 4 kg/cm in the first heavy transformation treatment 2 Or 5 kg/cm 2 The temperature was 200 ℃.
3. The method of manufacturing chemical manganese dioxide according to claim 1, wherein in the second densification treatment, the following steps are adopted: mnO (MnO) 2 ∶MnSO 4 ＝1∶0.195，MnO 2 ∶H 2 SO 4 （1.84）＝1∶0.09，MnO 2 ∶NaClO 3 ＝1∶0.138。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100201 CN1013434B (en) | 1988-01-11 | 1988-01-11 | Method for producing chemical manganese dioxide for battery |
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|---|---|---|---|
| CN 88100201 CN1013434B (en) | 1988-01-11 | 1988-01-11 | Method for producing chemical manganese dioxide for battery |
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| CN1034185A CN1034185A (en) | 1989-07-26 |
| CN1013434B true CN1013434B (en) | 1991-08-07 |
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| CN102107909B (en) * | 2011-01-11 | 2012-07-25 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous nano manganese dioxide |
| CN109205678B (en) * | 2018-10-10 | 2020-04-10 | 北京科技大学 | Method for preparing high apparent density chemical manganese dioxide |
| CN114105206A (en) * | 2021-11-25 | 2022-03-01 | 贵州大龙汇成新材料有限公司 | Preparation method of zinc-manganese dry battery active material |
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