CN117756080A - Preparation method of high-purity ammonium manganese phosphate and product thereof - Google Patents
Preparation method of high-purity ammonium manganese phosphate and product thereof Download PDFInfo
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- CN117756080A CN117756080A CN202311786185.9A CN202311786185A CN117756080A CN 117756080 A CN117756080 A CN 117756080A CN 202311786185 A CN202311786185 A CN 202311786185A CN 117756080 A CN117756080 A CN 117756080A
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- JLUGKDWGQPNDGX-UHFFFAOYSA-L azanium;manganese(2+);phosphate Chemical compound [NH4+].[Mn+2].[O-]P([O-])([O-])=O JLUGKDWGQPNDGX-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000000243 solution Substances 0.000 claims abstract description 63
- 239000002002 slurry Substances 0.000 claims abstract description 49
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011572 manganese Substances 0.000 claims abstract description 46
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 43
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 33
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 33
- 239000006012 monoammonium phosphate Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000003929 acidic solution Substances 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011656 manganese carbonate Substances 0.000 claims description 12
- 229940093474 manganese carbonate Drugs 0.000 claims description 12
- 235000006748 manganese carbonate Nutrition 0.000 claims description 12
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 12
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 12
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- MQMHJMFHCMWGNS-UHFFFAOYSA-N phosphanylidynemanganese Chemical compound [Mn]#P MQMHJMFHCMWGNS-UHFFFAOYSA-N 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229940102253 isopropanolamine Drugs 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 3
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 230000001276 controlling effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of high-purity ammonium manganese phosphate and a product thereof, relates to the technical field of chemical preparation of battery materials, and aims to solve the problem that the purity of the product is not high enough in the existing preparation method of ammonium manganese phosphate; mixing a manganese source with deionized water to obtain manganese source slurry; dissolving monoammonium phosphate in deionized water to obtain monoammonium phosphate solution; adding monoammonium phosphate solution into a reaction kettle, adding a catalyst, a reducing agent and a surfactant, and then adding manganese source slurry; adjusting the pH value by using an acidic solution and/or an alkaline solution, and stirring and reacting at 20-90 ℃; adding a reducing agent in the reaction process, and obtaining ammonium manganese phosphate slurry after the reaction is completed; the manganese ammonium phosphate slurry is filtered, rinsed and dried to obtain a manganese ammonium phosphate powder product; the method has the advantages of simple and easily controlled process steps, lower production cost, high product purity, less impurities and easy application to large-scale production.
Description
Technical Field
The invention relates to the technical field of chemical preparation of battery materials, in particular to a preparation method of high-purity ammonium manganese phosphate and a product thereof.
Background
Ammonium manganese phosphate of the formula NH 4 MnPO 4 ·H 2 O is an important chemical raw material, is widely applied to the fields of fertilizers, catalysts, flame retardants and the like, and particularly shows unique value in the preparation of lithium ion batteries as a precursor of the positive electrode material of the lithium ion batteries.
However, the conventional preparation method of the ammonium manganese phosphate has some remarkable defects such as low purity, low production efficiency, high cost and high energy consumption. In the existing preparation method, mn 2+ Is a major problem in oxidation of Mn during the reaction 2+ Is easily oxidized to Mn 3+ And Mn of 4+ Resulting in a decrease in product purity. In addition, the manganese source used in the conventional method is mainly sulfate or chloride of manganese, which can cause residual sulfate and chloride ions in the reaction product, for example, the publication number is CN115231544a, the preparation method of manganese ammonium phosphate and the invention patent application of lithium ion battery cathode material are disclosed, wherein the oxidation is reduced by adopting an antioxidant to produce high-valence manganese, but the method still cannot control the impurity content at a lower level, the purity is only 99.5% at most, and in addition, the process steps are relatively complex to control, so that the method is unfavorable for large-scale production.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity ammonium manganese phosphate and a product thereof, which are used for solving the problem that the purity of the product is not high enough in the existing preparation method of ammonium manganese phosphate.
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the high-purity ammonium manganese phosphate comprises the following steps:
step S1: mixing a manganese source with deionized water to obtain manganese source slurry;
step S2: dissolving monoammonium phosphate in deionized water to obtain monoammonium phosphate solution;
step S3: adding monoammonium phosphate solution into a reaction kettle, adding a catalyst, a reducing agent and a surfactant, and then adding manganese source slurry;
step S4: adjusting the pH value by using an acidic solution and/or an alkaline solution, and stirring and reacting at 20-90 ℃;
step S5: adding a reducing agent in the reaction process, and obtaining ammonium manganese phosphate slurry after the reaction is completed;
step S6: and (5) filtering, rinsing and drying the ammonium manganese phosphate slurry to obtain an ammonium manganese phosphate powder product.
Preferably, in the step S1, the manganese source is electrolytic metal manganese powder or/and high-purity manganese carbonate powder, and the manganese source is sieved by a 200-mesh sieve before preparing slurry; the solid content of the manganese source slurry is 30-60%.
Preferably, in the step S2, the concentration of the monoammonium phosphate solution is 1 to 3mol/L.
Preferably, in the steps S1 and S2, the impurity content of K, ca, na, mg of the manganese source is 100ppm or less, and the impurity content of the heavy metal Zn, cu, ni, pb is 10ppm or less; the content of heavy metal impurity Zn, cu, ni, pb of monoammonium phosphate is below 10 ppm.
Preferably, in the step S3, the catalyst is one or more of ammonia water, triethanolamine, propanolamine and isopropanolamine, the adding amount of the catalyst is 0.5-1% of the weight of the manganese source, the surfactant is one or more of sodium stearate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate and sodium dodecyl benzene sulfonate, and the adding amount of the surfactant is 0.05-0.1% of the weight of the manganese source; in the steps S3 and S5, the reducing agent is one or more of hydrogen peroxide, glucose, formaldehyde and acetaldehyde, the adding amount of the reducing agent in the step S3 is 1-2% of the weight of the manganese source, the adding amount of the reducing agent in the step S5 is 2-3% of the weight of the manganese source, and the supplementing time is 3 hours after the reaction.
Preferably, in the step S4, the acidic solution is one or more of phosphoric acid, formic acid, acetic acid and citric acid, the concentration of the acidic solution is 1-6 mol/L, the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia solution, and the concentration of the alkaline solution is 1-6 mol/L; and regulating the pH value of the reaction base solution to 3-6.
Preferably, the temperature of the reaction is 30-50 ℃, and the stirring speed is 200-500 rpm.
Preferably, the total time for the reaction is 12-18 hours, and the reaction is carried out for 1 hour after the reaction is free of bubbles.
Preferably, in the step S6, the rinsing is repeated at least 3 times with pure water to remove the free other ions.
The invention provides another technical scheme that: the product prepared by the preparation method, namely the manganese ammonium phosphate, has the impurity content of less than 0.05 percent, wherein the impurity S content is less than 250ppm, the impurity Cl < - > is less than 200ppm, the manganese-phosphorus ratio is 0.98-1, and the specific surface area is 1-20 m 2 /g。
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the high-purity ammonium manganese phosphate and the product thereof adopt a high-efficiency reaction way, manganese carbonate or manganese metal is used as a raw material, a catalyst, a reducing agent and a surfactant are added at a proper temperature, and the product generation is regulated and controlled by controlling the pH value.
2. According to the preparation method of the high-purity manganese ammonium phosphate and the product thereof, manganese ions can be effectively controlled to be oxidized by adding the reducing agent twice in the reaction, the progress of the reaction can be controlled by adding the catalyst and the surfactant, the prepared manganese ammonium phosphate product is high in purity and uniform in particle size distribution, the preparation of the precursor raw material of the lithium iron manganese phosphate battery is well adapted, and the quality and the application range of the product are greatly improved.
3. The preparation method of the high-purity ammonium manganese phosphate has the advantages that the process steps are simple, the raw materials are only required to be mixed after being prepared, the pH is adjusted, the stirring reaction is carried out, other control conditions are not needed except for the addition of the primary reducing agent in the process, the operation is convenient, reliable and easy to control, special equipment is not needed except for a reaction kettle, the raw materials are cheap and easy to obtain, the production cost is low, and the preparation method is easy to be applied to large-scale production.
Drawings
FIG. 1 is an SEM image of ammonium manganese phosphate prepared according to example 1 of the invention.
Fig. 2 is an SEM image of the ammonium manganese phosphate prepared in comparative example 1.
Fig. 3 is a schematic diagram comparing the XRD pattern and standard pattern of the ammonium manganese phosphate shown in fig. 1.
Detailed Description
The preparation method of the high-purity ammonium manganese phosphate comprises the following steps:
step S1: mixing a manganese source with deionized water to obtain manganese source slurry, wherein in a preferred embodiment, the manganese source adopts electrolytic metal manganese powder or/and high-purity manganese carbonate powder, and the manganese source is sieved by a 200-mesh sieve before preparing the slurry; the solid content of the manganese source slurry is preferably further controlled to be 30-60%; in addition, in order to further control the product impurities, the impurity content of the raw materials is preferably controlled slightly, so that the K, ca, na, mg impurity content of the manganese source is preferably below 100ppm, and the content of the heavy metal impurity Zn, cu, ni, pb is preferably below 10 ppm;
step S2: dissolving monoammonium phosphate in deionized water to obtain monoammonium phosphate solution, wherein the concentration of the monoammonium phosphate solution is preferably 1-3 mol/L, and regarding the impurity content of monoammonium phosphate raw material, the content of heavy metal impurity Zn, cu, ni, pb can be mainly concerned to be below 10 ppm;
step S3: adding monoammonium phosphate solution into a reaction kettle, adding a catalyst, a reducing agent and a surfactant, and then adding manganese source slurry, wherein the catalyst can be one or more of ammonia water, triethanolamine, propanolamine and isopropanolamine, the adding amount of the catalyst can be further controlled to be 0.5-1% of the weight of the manganese source, the surfactant can be one or more of sodium stearate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate and sodium dodecyl benzene sulfonate, the adding amount of the surfactant can be further controlled to be 0.05-0.1% of the weight of the manganese source, the reducing agent can be one or more of hydrogen peroxide, glucose, formaldehyde and acetaldehyde, and the adding amount of the reducing agent can be further controlled to be 1-2% of the weight of the manganese source;
step S4: adjusting the pH value by using an acidic solution and/or an alkaline solution, wherein the acidic solution can be one or more of phosphoric acid, formic acid, acetic acid and citric acid, the concentration of the acidic solution can be 1-6 mol/L, the alkaline solution can be one or more of a sodium hydroxide solution, a potassium hydroxide solution and an ammonia water solution, and the concentration of the alkaline solution can be 1-6 mol/L; adjusting the pH value of the reaction base solution to 3-6, stirring and reacting at 20-90 ℃, preferably at 30-50 ℃, and stirring at 200-500 rpm for reference;
step S5: adding a reducing agent in the reaction process, wherein the reducing agent can be one or more of hydrogen peroxide, glucose, formaldehyde and acetaldehyde, the adding amount of the reducing agent can be further controlled to be 2-3% of the weight of a manganese source, the adding time is preferably 3 hours after the reaction is carried out, the ammonium manganese phosphate slurry is obtained after the reaction is completed, the total reaction time is generally 5-25 hours, more preferably 12-18 hours, and the specific complete reaction control is that the reaction is regarded as complete after no bubbles are generated;
step S6: the manganese ammonium phosphate slurry is filtered, rinsed and dried to obtain a manganese ammonium phosphate powder product; wherein rinsing is preferably repeated at least 3 times with pure water for removing free other ions.
Note that: generally, in the above process, the reference of the ratio of manganese source to monoammonium phosphate is 1:1, but the ratio can also be changed in a certain range in actual production, so that the control of ingredients is convenient, for example, the ratio of manganese to phosphorus is 1:0.95-1.2.
Example 1:
(1) Mixing 1149.5g of manganese carbonate which passes through a 200-mesh screen with deionized water according to the solid content of 40% to obtain manganese carbonate slurry;
(2) Preparing 5L of 2mol/L monoammonium phosphate solution, 1mol/L ammonia water solution and 1mol/L phosphoric acid solution by using deionized water;
(3) Adding the monoammonium phosphate solution in the step (2) into a 20L reaction kettle, adding 6g of ammonia water, 40g of 30% hydrogen peroxide solution and 1g of sodium stearate into the solution, and adding the slurry in the step (1).
(4) And (3) adding the phosphoric acid solution in the step (2) into a reaction kettle, continuously adjusting the pH to 3.5, controlling the stirring speed in the reaction process to be 500rpm, and uniformly stirring at the reaction temperature of 35 ℃.
(5) 80g of 30% hydrogen peroxide solution is added in the reaction for 18 hours, and the ammonium manganese phosphate slurry is obtained after the reaction is completed;
(6) And (3) filtering, rinsing for 3 times and drying the ammonium manganese phosphate slurry obtained in the step (5), and then drying the filtered product in a 70 ℃ oven to obtain an ammonium manganese phosphate powder product.
SEM and XRD patterns of the ammonium manganese phosphate product prepared in example 1 are shown in fig. 1 and 3, respectively; as can be seen from fig. 1, the ammonium manganese phosphate has a uniform particle size distribution.
Example 2:
(1) 550g of metal manganese which passes through a 200-mesh screen is mixed with deionized water according to the solid content of 40% to obtain metal manganese slurry;
(2) Preparing 5L of 2mol/L monoammonium phosphate solution, 1mol/L ammonia water solution and 1mol/L phosphoric acid solution by using deionized water;
(3) Adding the monoammonium phosphate solution in the step (2) into a 20L reaction kettle, adding 6g of triethanolamine, 40g of 30% hydrogen peroxide solution and 1g of sodium stearate into the solution, and adding the slurry in the step (1).
(4) And (3) adding the phosphoric acid solution in the step (2) into a reaction kettle, continuously adjusting the pH to 3.5, controlling the stirring speed in the reaction process to be 500rpm, and uniformly stirring at the reaction temperature of 35 ℃.
(5) 80g of 30% hydrogen peroxide solution is added in the reaction for 18 hours, and the ammonium manganese phosphate slurry is obtained after the reaction is completed;
(6) And (3) filtering, rinsing for 3 times and drying the ammonium manganese phosphate slurry obtained in the step (5), and then drying the filtered product in a 70 ℃ oven to obtain an ammonium manganese phosphate powder product.
Example 3:
(1) Mixing 1149.5g of manganese carbonate which passes through a 200-mesh screen with deionized water according to the solid content of 40% to obtain manganese carbonate slurry;
(2) Preparing 5L of 2mol/L monoammonium phosphate solution, 1mol/L ammonia water solution and 1mol/L phosphoric acid solution by using deionized water;
(3) Adding the monoammonium phosphate solution in the step (2) into a 20L reaction kettle, adding 6g of triethanolamine, 40g of 30% hydrogen peroxide solution and 1g of sodium stearate into the solution, and adding the slurry in the step (1).
(4) And (3) adding the phosphoric acid solution in the step (2) into a reaction kettle, continuously adjusting the pH to 3.5, controlling the stirring speed in the reaction process to be 500rpm, and uniformly stirring at the reaction temperature of 45 ℃.
(5) 80g of 30% hydrogen peroxide solution is added in the reaction for 18 hours, and the ammonium manganese phosphate slurry is obtained after the reaction is completed;
(6) And (3) filtering, rinsing for 3 times and drying the ammonium manganese phosphate slurry obtained in the step (5), and then drying the filtered product in a 70 ℃ oven to obtain an ammonium manganese phosphate powder product.
Example 4:
(1) Mixing 1149.5g of manganese carbonate which passes through a 200-mesh screen with deionized water according to the solid content of 40% to obtain manganese carbonate slurry;
(2) Preparing 5L of 2mol/L monoammonium phosphate solution, 1mol/L ammonia water solution and 1mol/L phosphoric acid solution by using deionized water;
(3) Adding the monoammonium phosphate solution in the step (2) into a 20L reaction kettle, adding 6g of triethanolamine, 40g of 30% hydrogen peroxide solution and 1g of sodium stearate into the solution, and adding the slurry in the step (1).
(4) And (3) adding the phosphoric acid solution in the step (2) into a reaction kettle, continuously adjusting the pH to 3.8, controlling the stirring speed in the reaction process to be 500rpm, and uniformly stirring at the reaction temperature of 35 ℃.
(5) 80g of 30% hydrogen peroxide solution is added in the reaction for 18 hours, and the ammonium manganese phosphate slurry is obtained after the reaction is completed;
(6) And (3) filtering, rinsing for 3 times and drying the ammonium manganese phosphate slurry obtained in the step (5), and then drying the filtered product in a 70 ℃ oven to obtain an ammonium manganese phosphate powder product.
Example 5:
(1) Mixing 1149.5g of manganese carbonate which passes through a 200-mesh screen with deionized water according to the solid content of 40% to obtain manganese carbonate slurry;
(2) Preparing 5L of 2mol/L monoammonium phosphate solution, 1mol/L ammonia water solution and 1mol/L phosphoric acid solution by using deionized water;
(3) Adding the monoammonium phosphate solution in the step (2) into a 20L reaction kettle, adding 6g of triethanolamine, 40g of 30% hydrogen peroxide solution and 1g of sodium stearate into the solution, and adding the slurry in the step (1).
(4) And (3) adding the phosphoric acid solution in the step (2) into a reaction kettle, continuously adjusting the pH to 3, controlling the stirring speed in the reaction process to be 500rpm, and uniformly stirring at the reaction temperature of 35 ℃.
(5) 80g of 30% hydrogen peroxide solution is added in the reaction for 18 hours, and the ammonium manganese phosphate slurry is obtained after the reaction is completed;
(6) And (3) filtering, rinsing for 3 times and drying the ammonium manganese phosphate slurry obtained in the step (5), and then drying the filtered product in a 70 ℃ oven to obtain an ammonium manganese phosphate powder product.
Example 6:
(1) 550g of metal manganese which passes through a 200-mesh screen is mixed with deionized water according to the solid content of 40% to obtain metal manganese slurry;
(2) Preparing 5L of 2mol/L monoammonium phosphate solution, 1mol/L ammonia water solution and 1mol/L phosphoric acid solution by using deionized water;
(3) Adding the monoammonium phosphate solution in the step (2) into a 20L reaction kettle, adding 6g of triethanolamine, 40g of 30% hydrogen peroxide solution and 1g of sodium stearate into the solution, and adding the slurry in the step (1).
(4) And (3) adding the phosphoric acid solution in the step (2) into a reaction kettle, continuously adjusting the pH to 4, controlling the stirring speed in the reaction process to be 500rpm, and uniformly stirring at the reaction temperature of 35 ℃.
(5) 80g of 30% hydrogen peroxide solution is added in the reaction for 18 hours, and the ammonium manganese phosphate slurry is obtained after the reaction is completed;
(6) And (3) filtering, rinsing for 3 times and drying the ammonium manganese phosphate slurry obtained in the step (5), and then drying the filtered product in a 70 ℃ oven to obtain an ammonium manganese phosphate powder product.
Comparative example 1:
(1) Preparing 10L of 1mol/L battery-grade manganese sulfate solution by deionized water;
(2) Preparing 5L of 2mol/L monoammonium phosphate solution, 1mol/L ammonia water solution and 1mol/L phosphoric acid solution by using deionized water;
(3) Adding the monoammonium phosphate solution in the step (2) into a 20L reaction kettle, adding 6g of ammonia water, 40g of 30% hydrogen peroxide solution and 1g of sodium stearate into the solution, and adding the slurry in the step (1).
(4) And (3) adding the phosphoric acid solution in the step (2) into a reaction kettle, continuously adjusting the pH to 3.5, controlling the stirring speed in the reaction process to be 500rpm, and uniformly stirring at the reaction temperature of 35 ℃.
(5) 80g of 30% hydrogen peroxide solution is added in the reaction for 18 hours, and the ammonium manganese phosphate slurry is obtained after the reaction is completed;
(6) And (3) filtering, rinsing for 3 times and drying the ammonium manganese phosphate slurry obtained in the step (5), and then drying the filtered product in a 70 ℃ oven to obtain an ammonium manganese phosphate powder product.
The SEM image of the ammonium manganese phosphate product prepared in comparative example 1 is shown in fig. 2, and it is obvious that the uneven particle size distribution may cause uneven product quality.
The physicochemical indexes of the products obtained in the examples and comparative examples are shown in the following Table 1:
TABLE 1 physicochemical index of manganese ammonium phosphate
As can be seen from Table 1, the purity of the ammonium manganese phosphate prepared by the method of the invention is higher than 99.95%, namely the impurity content is lower than 0.05%, wherein the impurity S content is lower than 250ppm, the impurity Cl-is lower than 200ppm, the manganese-phosphorus ratio is 0.98-1, and the specific surface area is 1-20 m 2 /g; the purity of the ammonium manganese phosphate prepared in the prior art is difficult to reach the height of the invention, and through a large number of preparation experiments of different methods, the S content is basically 1 to 2 kiloppm, and the manganese-phosphorus ratio is generally more than 1.0, and various indexes are difficult to meet the demands of downstream customers, so that the method and the product of the invention are obviously better.
The above is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be covered by the present invention. Therefore, the protection scope of the present invention should be defined by the claims.
The present invention is not described in detail in the present application, and is well known to those skilled in the art.
Claims (10)
1. The preparation method of the high-purity ammonium manganese phosphate is characterized by comprising the following steps of:
step S1: mixing a manganese source with deionized water to obtain manganese source slurry;
step S2: dissolving monoammonium phosphate in deionized water to obtain monoammonium phosphate solution;
step S3: adding monoammonium phosphate solution into a reaction kettle, adding a catalyst, a reducing agent and a surfactant, and then adding manganese source slurry;
step S4: adjusting the pH value by using an acidic solution and/or an alkaline solution, and stirring and reacting at 20-90 ℃;
step S5: adding a reducing agent in the reaction process, and obtaining ammonium manganese phosphate slurry after the reaction is completed;
step S6: and (5) filtering, rinsing and drying the ammonium manganese phosphate slurry to obtain an ammonium manganese phosphate powder product.
2. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: in the step S1, the manganese source is electrolytic metal manganese powder or/and high-purity manganese carbonate powder, and the manganese source is sieved by a 200-mesh sieve before preparing slurry; the solid content of the manganese source slurry is 30-60%.
3. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: in the step S2, the concentration of the monoammonium phosphate solution is 1-3 mol/L.
4. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: in the steps S1 and S2, the K, ca, na, mg impurity content of the manganese source is below 100ppm, and the content of the heavy metal impurity Zn, cu, ni, pb is below 10 ppm; the content of heavy metal impurity Zn, cu, ni, pb of monoammonium phosphate is below 10 ppm.
5. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: in the step S3, the catalyst is one or more of ammonia water, triethanolamine, propanolamine and isopropanolamine, the adding amount of the catalyst is 0.5-1% of the weight of the manganese source, the surfactant is one or more of sodium stearate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate and sodium dodecyl benzene sulfonate, and the adding amount of the surfactant is 0.05-0.1% of the weight of the manganese source; in the steps S3 and S5, the reducing agent is one or more of hydrogen peroxide, glucose, formaldehyde and acetaldehyde, the adding amount of the reducing agent in the step S3 is 1-2% of the weight of the manganese source, the adding amount of the reducing agent in the step S5 is 2-3% of the weight of the manganese source, and the supplementing time is 3 hours after the reaction.
6. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: in the step S4, the acidic solution is one or more of phosphoric acid, formic acid, acetic acid and citric acid, the concentration of the acidic solution is 1-6 mol/L, the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water solution, and the concentration of the alkaline solution is 1-6 mol/L; and regulating the pH value of the reaction base solution to 3-6.
7. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: the reaction temperature is 30-50 ℃, and the stirring rotation speed is 200-500 rpm.
8. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: the total time of the reaction is 12-18 h, and the reaction is carried out for 1 hour after no bubble exists.
9. The method for preparing high-purity ammonium manganese phosphate according to claim 1, which is characterized in that: in the step S6, rinsing is repeated at least 3 times with pure water to remove other ions.
10. A product produced by the process for producing high purity ammonium manganese phosphate according to any one of claims 1 to 9, characterized in that: the product is manganese ammonium phosphate, the impurity content is lower than 0.05%, wherein the impurity S content is lower than 250ppm, and the impurity Cl is - Less than 200ppm, the manganese-phosphorus ratio is 0.98-1, the specific surface area is 1-20 m 2 /g。
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