CN113998743A - Manganese-rich hydroxide precursor and preparation method and application thereof - Google Patents
Manganese-rich hydroxide precursor and preparation method and application thereof Download PDFInfo
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- CN113998743A CN113998743A CN202111248011.8A CN202111248011A CN113998743A CN 113998743 A CN113998743 A CN 113998743A CN 202111248011 A CN202111248011 A CN 202111248011A CN 113998743 A CN113998743 A CN 113998743A
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Abstract
The invention provides a manganese-rich hydroxide precursor and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing manganese salt, cobalt salt and nickel salt to obtain mixed salt solution; mixing ammonia water, alkali liquor, an additive and a mixed salt solution to obtain a raw material solution; heating and stirring the raw material solution, and controlling the pH value to obtain a precipitate; and washing and drying are sequentially carried out to obtain the manganese-rich hydroxide precursor. The preparation method provided by the invention does not need to introduce nitrogen, so that the problem of fluctuation of system volume and liquid-solid contact area is avoided, the reaction slurry is stable, and the preparation method is favorable for obtaining the manganese-rich hydroxide precursor with uniform components. The additive is added into the raw materials, so that the oxidation of manganese by dissolved oxygen in the raw materials is avoided, and the condition that MnOOH is not generated in the synthesis process is ensured, so that a manganese-rich hydroxide precursor with no oxidation and high capacity can be obtained; meanwhile, bulk phase doping can be realized, the rear end doping process is reduced, and the doping uniformity is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, relates to a preparation method of a precursor, and particularly relates to a manganese-rich hydroxide precursor as well as a preparation method and application thereof.
Background
Preparation of manganese-rich hydroxide precursorThe capacity of the obtained lithium-rich manganese-based positive electrode material is low, the main reason is that a manganese-rich hydroxide precursor is difficult to synthesize, manganese is easy to oxidize during precipitation in the process of preparing the manganese-rich hydroxide by adopting a coprecipitation method, the oxidized manganese forms MnOOH and is difficult to coprecipitate with hydroxide of Ni or Co, and solid solution type Li required by the lithium-rich manganese-based positive electrode material is difficult to form after sintering2MnO3Phase, therefore, resulting in a lower capacity.
The phenomenon of manganese element oxidation is easy to occur in the preparation of the manganese-rich hydroxide, and the general improvement scheme is that a large amount of nitrogen is introduced to avoid the contact of manganese and air so as to reduce the oxidation, but the dissolved oxygen in the raw materials is difficult to remove, and the cost is higher; in actual mass production, oxidation phenomenon still exists, and after the precipitate is oxidized, new precipitate is continuously oxidized, all precipitates are oxidized, and the waste rate is high.
CN 110963533a discloses a preparation method of a precursor of a lithium-rich manganese-based positive electrode material, comprising the following steps: selecting raw materials; filtering to remove impurities; carrying out parallel flow reaction; processing a product; inspecting the quality of the sample; in the first step, a metal salt solution, an ammonia-soda mixed solution and a protective gas are selected as raw materials, wherein a manganese salt, a nickel salt and a cobalt salt are dissolved in deionized water according to a certain stoichiometric ratio; adding an additive with low cost when materials are synthesized, preparing spherical particles of a lithium-rich manganese-based material precursor with a special shape by controlling synthesis conditions, washing, filtering, drying, uniformly mixing with a lithium salt, sintering and sieving to obtain the lithium-rich manganese-based positive electrode material with excellent cycle performance; the prepared precursor of the lithium-rich manganese-based hydroxide system has low production cost and excellent cycle performance after being sintered into the anode, and is suitable for mass production.
CN 109860561A discloses a lithium-manganese-boron-rich hollow microsphere prepared by treating metal hydroxide sol with boron hydrides such as sodium borohydride, forming Ni-Co-B alloy microspheres in the core of a precursor and wrapping a manganese-rich outer layer on the surface.
CN 102646828A discloses a method for preparing anode material LiMnPO of lithium ion battery4Method of/C, kitThe method comprises the following steps: mixing a lithium source, a high-valence manganese source and a phosphorus source with lithium, manganese and phosphorus, wherein the valence state of manganese ions in the high-valence manganese source is more than 2; adding organic carbon source additive, and mechanically activating and reducing at 5-35 deg.C for 0.5-20 hr to reduce high-valence manganese into divalent manganese and prepare amorphous LiMnPO4Heating the precursor to 400-800 ℃ in a non-oxidizing atmosphere, and keeping the temperature for 0.5-12h to obtain pure-phase LiMnPO4And C, material. In the mechanical activation process, all elements are mixed at the atomic level and high-valence manganese is reduced, and LiMnPO is directly prepared4Precursor, excessive organic additive in the sintering process to inhibit the growth of particles, thereby preparing LiMnPO with excellent performance4The first discharge specific capacity of 1C of the material/C is more than 100 mAh/g.
In the above prior art, the oxidation state of high-valence manganese is prevented from being obtained by non-oxidizing gas and additives, however, CN 110963533a does not discuss the type and dosage of additives and the obtained effect, CN 109860561a uses sodium borohydride to dope the lithium-rich manganese-based material, and adds the sodium borohydride in the process and the obtained doping effect, so that oxidation of Mn inside the precursor cannot be effectively avoided, and the step of specially performing reduction activation in the method disclosed in CN 102646828A cannot ensure that Mn is not oxidized in the oxidation precipitation process of the manganese element.
Therefore, how to inhibit the oxidation of manganese by introducing a proper additive in the preparation of a precursor of a positive electrode material with high manganese hydroxide content so as to Co-precipitate Mn, Ni, Co and other elements is a problem which needs to be solved urgently in preparing a high-capacity lithium-rich positive electrode material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a manganese-rich hydroxide precursor and a preparation method and application thereof. The additive is added into the raw materials to inhibit the oxidation of manganese, so that Mn is coprecipitated with elements such as Ni and Co, and a manganese-rich hydroxide precursor with uniformly distributed elements is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of a manganese-rich hydroxide precursor, comprising the following steps:
(1) mixing manganese salt, cobalt salt and nickel salt to obtain mixed salt solution;
(2) mixing ammonia water, alkali liquor, an additive and the mixed salt solution obtained in the step (1) to obtain a raw material solution;
(3) heating and stirring the raw material solution obtained in the step (2), and controlling the pH value to obtain a precipitate;
(4) and (4) washing and drying the precipitate obtained in the step (3) in sequence to obtain the manganese-rich hydroxide precursor.
According to the method for preparing the manganese-rich hydroxide precursor by wet reduction precipitation, the additive is added, so that the existence of dissolved oxygen in the raw material is avoided, and the oxidation of manganese is fundamentally inhibited.
According to the method for preparing the manganese-rich hydroxide precursor by wet reduction and precipitation, non-oxidizing gases such as nitrogen and the like or other inert gases are not required to be introduced in the reaction process, the sealing property of a container in the reaction process is not required to be controlled, relatively stable slurry in the reaction process can be obtained, and the fluctuation of the system volume and the liquid-solid contact area caused by gas introduction is effectively prevented.
Preferably, the molar ratio of manganese, cobalt and nickel Mn: Co: Ni in the mixed salt solution described in step (1) is x: y (1-x-y), where 0.4. ltoreq. x.ltoreq.1, 0. ltoreq. y.ltoreq.0.3, for example x may be 0.4, 0.6, 0.7, 0.8 or 1, for example y may be 0, 0.05, 0.1, 0.15, 0.2 or 0.3, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
Preferably, the mixed salt solution of step (1) has a mixed salt concentration of 1-2mol/L, such as 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L or 2mol/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the concentration of the ammonia water in the step (2) is 5-25% by mass, for example, it can be 5%, 10%, 15%, 20% or 25% by mass, but it is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the alkali liquor in step (2) is an alkali metal hydroxide solution.
Preferably, the alkali metal hydroxide comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide or lithium hydroxide, typical but non-limiting combinations include sodium hydroxide in combination with potassium hydroxide, sodium hydroxide in combination with lithium hydroxide, potassium hydroxide in combination with lithium hydroxide, and sodium hydroxide, potassium hydroxide in combination with lithium hydroxide.
Preferably, the alkali metal hydroxide solution has a concentration of 4 to 8mol/L, which may be, for example, 4mol/L, 5mol/L, 6mol/L, 7mol/L or 8mol/L, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the additive in step (2) comprises any one or a combination of at least two of sodium hypophosphite, sodium borohydride, formaldehyde, lithium borohydride, nickel borohydride or sodium sulfite, and typical but non-limiting combinations include sodium hypophosphite and sodium borohydride, sodium borohydride and formaldehyde, nickel borohydride and sodium sulfite, sodium hypophosphite, sodium borohydride and formaldehyde, and lithium borohydride, nickel borohydride and sodium sulfite.
Preferably, the additives in step (2) are mixed after being prepared into a solution.
Preferably, the concentration of the additive in step (2) is 0.01-5mol/L, such as 0.01mol/L, 1mol/L, 2.5mol/L, 3mol/L or 5mol/L, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The additive type and concentration provided by the invention can effectively prevent manganese from being oxidized, and simultaneously are beneficial to invading precursor doping, so that bulk doping is realized in a precursor process section, subsequent doping procedures are reduced, and doping is more uniform.
Preferably, sodium hypophosphite is used as an additive, the concentration of the additive is 0.01-0.4mol/L, the sodium hypophosphite can effectively reduce 4-valent manganese in an alkaline environment, but the excessive concentration can further reduce the manganese into monovalent manganese, and in the reduction process, the hypophosphite is oxidized into phosphate to be embedded into a structure to form phosphate complex, so that bulk phase doping of P element is realized;
preferably, formaldehyde is used as an additive, the concentration of the additive is 0.1-1mol/L, tetravalent manganese can be effectively reduced, and other elements are not introduced;
preferably, a sodium sulfite additive is used, the concentration of the additive is 0.2-2mol/L, tetravalent manganese can be effectively reduced, sodium sulfate is generated, and the influence on the system is small.
Preferably, the concentration of ammonia in the feed solution in step (2) is 0.02-1mol/L, and may be, for example, 0.02mol/L, 0.1mol/L, 0.5mol/L, 0.75mol/L or 1mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the concentration of the additive in the raw material solution in step (2) is 0.001-2mol/L, for example, 0.001mol/L, 0.01mol/L, 0.2mol/L, 1mol/L or 2mol/L, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the temperature of the heating and stirring in step (3) is 50-70 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the rotation speed of the heating and stirring in step (3) is 300-800r/min, such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min or 800r/min, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the heating and stirring time in step (3) is 6-48h, such as 4h, 8h, 15h, 20h, 30h, 40h or 48h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the pH in step (3) is 9-12, and may be, for example, 9, 10, 10.5, 11 or 12, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
The pH of the raw material solution is determined by regulating the addition amount of the alkali metal solution.
Preferably, the precipitate obtained in step (3) has a particle size in the range of 3 to 10 μm.
Preferably, the washing detergent of step (4) comprises ethanol and/or diethyl ether.
Preferably, the drying temperature in step (4) is 90-120 ℃, for example, it may be 90 ℃, 100 ℃, 110 ℃, 115 ℃ or 120 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred technical solution of the first aspect of the present invention, the preparation method comprises the steps of:
(1) mixing manganese salt, cobalt salt and nickel salt to obtain mixed salt solution; the concentration of the mixed salt is 1-2mol/L, the molar ratio of manganese, cobalt and nickel in the mixed salt solution is Mn, Co, Ni and x, y and (1-x-y), wherein x is more than or equal to 0.4 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.3;
(2) mixing ammonia water, alkali liquor, an additive and the mixed salt solution obtained in the step (1) to obtain a raw material solution; the concentration of ammonia in the raw material solution is 0.02-1mol/L, and the concentration of the additive is 0.001-2 mol/L;
(3) heating and stirring the raw material solution obtained in the step (2), and controlling the pH to be 9-12 to obtain a precipitate with the particle size range of 3-10 mu m; the heating and stirring temperature is 50-70 ℃, the time is 6-48h, and the stirring speed is 300-;
(4) washing and drying the precipitate obtained in the step (3) to obtain the manganese-rich hydroxide precursor; the washed detergent comprises ethanol and/or diethyl ether, and the drying temperature is 90-120 ℃;
the mass percentage concentration of the ammonia water in the step (2) is 5-25%; the alkali liquor is an alkali metal hydroxide solution, the alkali metal hydroxide comprises any one or the combination of at least two of sodium hydroxide, potassium hydroxide or lithium hydroxide, and the concentration of the alkali metal hydroxide is 4-8 mol/L;
and (3) the additive in the step (2) comprises any one or combination of at least two of sodium hypophosphite, sodium borohydride, formaldehyde, lithium borohydride, nickel borohydride and sodium sulfite, and the additive is prepared into a solution to be mixed, wherein the concentration of the solution is 0.01-5 mol/L.
Second oneIn one aspect, the invention provides a manganese-rich hydroxide precursor obtained by the preparation method according to the first aspect, wherein the chemical formula of the manganese-rich hydroxide precursor is MnxCoyNi1-x-y(OH)2Wherein x is more than or equal to 0.4 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.3.
In a third aspect, the present invention provides a use of the manganese-rich hydroxide precursor according to the second aspect for a lithium ion battery.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method provided by the invention does not need to introduce nitrogen, so that the problems of system volume and liquid-solid contact area fluctuation do not occur, and the reaction slurry is stable;
(2) according to the invention, the additive is added into the raw materials, so that the manganese is prevented from being oxidized by dissolved oxygen in the raw materials in the preparation process, MnOOH is not generated in the synthesis process, and the manganese-rich hydroxide precursor with no oxidation and high capacity is prepared;
(3) according to the invention, the additive is added into the raw materials to prevent oxidation, and meanwhile, bulk phase doping can be realized in the preparation section of the precursor, so that the rear-end doping process is reduced, and the doping is more uniform.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of a manganese-rich hydroxide precursor, which comprises the following steps:
(1) mixing manganese sulfate monohydrate, cobalt sulfate heptahydrate, nickel sulfate hexahydrate and water to obtain a mixed salt solution, wherein the concentration of the mixed salt is 1.5mol/L, and the molar ratio of manganese, cobalt and nickel in the mixed salt solution is Mn, Co and Ni, x, y (1-x-y), wherein x is 0.4, and y is 0.3;
(2) mixing 15% ammonia water, 6mol/L sodium hydroxide solution, 2.5mol/L sodium hypophosphite solution and the mixed salt solution obtained in the step (1) in percentage by mass to obtain a raw material solution; in the process, the concentration of ammonia in the raw material solution is controlled to be 0.5mol/L, and the concentration of sodium hypophosphite is controlled to be 1 mol/L;
(3) heating and stirring the raw material solution obtained in the step (2) at the stirring speed of 550r/min at 60 ℃ for 24 hours, and controlling the pH to be 10.5 to obtain a precipitate with the particle size range of 3-10 mu m;
(4) washing with pure water and drying the precipitate obtained in the step (3) at 100 ℃ to obtain the manganese-rich hydroxide precursor.
Example 2
The embodiment provides a preparation method of a manganese-rich hydroxide precursor, which comprises the following steps:
(1) mixing manganese sulfate monohydrate, cobalt sulfate heptahydrate and nickel sulfate hexahydrate to obtain a mixed salt solution, wherein the concentration of the mixed salt is 1mol/L, and the molar ratio of manganese, cobalt and nickel in the mixed salt solution is Mn, Co, Ni, x, y (1-x-y), wherein x is 0.5, and y is 0.3;
(2) mixing 25% ammonia water, 4mol/L potassium hydroxide solution, additive and the mixed salt solution obtained in the step (1) to obtain a raw material solution; the additive is a mixed solution of sodium borohydride and formaldehyde according to the molar ratio of 1:1, and the concentration is 0.01 mol/L; in the process, the concentration of ammonia in the raw material solution is controlled to be 0.02mol/L, and the concentration of the additive is controlled to be 0.001 mol/L;
(3) heating and stirring the raw material solution obtained in the step (2) at the stirring speed of 300r/min at 50 ℃ for 48h, and controlling the pH to be 12 to obtain a precipitate with the particle size range of 3-10 mu m;
(4) washing with pure water and drying the precipitate obtained in the step (3) at 90 ℃ to obtain the manganese-rich hydroxide precursor.
Example 3
The embodiment provides a preparation method of a manganese-rich hydroxide precursor, which comprises the following steps:
(1) mixing manganese sulfate monohydrate, cobalt sulfate heptahydrate and nickel sulfate hexahydrate to obtain a mixed salt solution, wherein the concentration of the mixed salt is 2mol/L, and the molar ratio of manganese, cobalt and nickel in the mixed salt solution is Mn, Co, Ni, x, y (1-x-y), wherein x is 0.4, and y is 0.2;
(2) mixing ammonia water with the mass percentage concentration of 55%, lithium hydroxide solution with the concentration of 8mol/L, additive and the mixed salt solution obtained in the step (1) to obtain a raw material solution; the additive is a mixed solution of sodium borohydride, lithium borohydride and nickel borohydride according to the molar ratio of 1:1:1, and the concentration is 5 mol/L; in the process, the concentration of ammonia in the raw material solution is controlled to be 1mol/L, and the concentration of the additive is controlled to be 2 mol/L;
(3) heating and stirring the raw material solution obtained in the step (2) at the stirring speed of 800r/min at 70 ℃ for 6 hours, and controlling the pH to be 9 to obtain a precipitate with the particle size range of 3-10 mu m;
(4) washing with pure water and drying the precipitate obtained in the step (3) at 120 ℃ to obtain the manganese-rich hydroxide precursor.
Example 4
The embodiment provides a preparation method of a manganese-rich hydroxide precursor, and the steps and parameters of the other processes are the same as those of the embodiment 1 except that the additive in the step (2) is sodium borohydride.
Example 5
The embodiment provides a preparation method of a manganese-rich hydroxide precursor, and the steps and parameters of the other processes are the same as those of the embodiment 1 except that the additive in the step (2) is formaldehyde.
Example 6
The embodiment provides a preparation method of a manganese-rich hydroxide precursor, and the steps and parameters of the other processes are the same as those of the embodiment 1 except that the additive in the step (2) is nickel borohydride.
Example 7
This example provides a method for preparing a manganese-rich hydroxide precursor, which includes the same process steps and parameters as those in example 1, except that the additive in step (2) is sodium sulfite.
Example 8
The embodiment provides a preparation method of a manganese-rich hydroxide precursor, and the steps and parameters of the other processes are the same as those of the embodiment 1 except that the additive in the step (2) is oxalic acid.
Example 9
This example provides a method for preparing a manganese-rich hydroxide precursor, which includes the same process steps and parameters as those in example 1, except that the additive in step (2) is ascorbic acid.
Comparative example 1
The comparative example provides a preparation method of a manganese-rich hydroxide precursor, and the preparation method comprises the same process steps and parameters as those in example 1 except that no additive is added in the step (2), nitrogen is introduced in the heating and stirring process in the step (3), and the flow rate of the nitrogen is 100 mL/min.
Comparative example 2
The comparative example provides a preparation method of a manganese-rich hydroxide precursor, and the preparation method is the same as the preparation method of example 1 except that no additive is added in the step (2), and no nitrogen is introduced in the heating and stirring process in the step (3).
The manganese-rich hydroxide precursors obtained in examples 1 to 9 and comparative examples 1 to 2, and the manganese-rich cathode material prepared from the manganese-rich hydroxide precursors were tested. XRD test was performed on the manganese-rich hydroxide precursor using a bruker D8X radiation diffractometer, and capacitance test was performed on the manganese-rich positive electrode material using a blue test chamber, and the results obtained are shown in table 1.
TABLE 1
| Test number | Capacity (mAh/g) | Presence or absence of MnOOH phase |
| Example 1 | 259 | Whether or not |
| Example 2 | 251 | Whether or not |
| Example 3 | 248 | Whether or not |
| Example 4 | 252 | Whether or not |
| Example 5 | 256 | Whether or not |
| Example 6 | 250 | Whether or not |
| Example 7 | 257 | Whether or not |
| Example 8 | 210 | Is that |
| Example 9 | 218 | Is that |
| Comparative example 1 | 229 | Is that |
| Comparative example 2 | 173 | Is that |
The following conclusions are drawn from table 1:
the capacity of the product prepared by the existing manganese-rich hydroxide is 200-235 mAh/g under the conditions of 0.1C and 4.6-2.1V, the first effect is only 80-85%, and the main reason is that part of the precursor generates MnOOH, and the capacity is difficult to be increased to 250mAh/g in the subsequent sintering process. The difficulty that the high capacity is always hydroxide is realized only by changing the preparation process of the material without changing the components of the material; the method avoids forming MnOOH in the preparation process of the precursor, keeps the integrity of the layered structure of the precursor, and is beneficial to Li after sintering2MnO3The stability of structure helps promoting first effect, increases the capacity.
(1) From examples 1 to 3, it can be seen that the preparation method provided by the invention prevents the oxidation of manganese by the raw material dissolved oxygen by selecting appropriate additive types and concentrations, does not generate MnOOH in the synthesis process, and prepares the non-oxidation high-capacity manganese-rich hydroxide precursor.
(2) As can be seen from comparison of the results of examples 4 to 7 with example 1, the additive species provided by the present invention have a good reduction effect, and can effectively prevent oxidation of manganese during the preparation process, thereby preparing a manganese-rich hydroxide precursor having a high capacity and containing no MnOOH.
(3) From the results of examples 8 and 9 and example 1, it can be seen that when the kind of the additive is changed, the manganese-rich hydroxide precursor containing a small amount of MnOOH is prepared and the capacity is low, which indicates that the kind of the additive provided by the present invention is an important process step in the preparation method, and helps to prepare the manganese-rich hydroxide precursor which does not contain MnOOH and has high capacity.
(4) From the results of comparative examples 1-2 and example 1, it can be seen that the manganese-rich hydroxide precursor containing a small amount of MnOOH was prepared and the capacity was low when nitrogen gas was introduced during the preparation process without adding additives, which indicates that the preparation method provided by the present invention improves the defect that oxidation resistance is not effectively prevented by introducing nitrogen gas in the prior art, and the preparation method provided by the present invention prepares a manganese-rich hydroxide precursor containing no MnOOH and having high capacity.
In conclusion, the preparation method provided by the invention does not need to introduce nitrogen, so that the problems of system volume and liquid-solid contact area fluctuation are avoided, the reaction slurry is stable, and the preparation method is favorable for obtaining the manganese-rich hydroxide precursor with uniform components. In addition, the additive is added into the raw materials, so that the oxidation of manganese by dissolved oxygen in the raw materials is avoided, and the condition that MnOOH is not generated in the synthesis process is ensured, so that a manganese-rich hydroxide precursor with no oxidation and high capacity can be obtained; meanwhile, the addition of the additive can realize bulk phase doping, reduce the rear end doping process and improve the doping uniformity.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the manganese-rich hydroxide precursor is characterized by comprising the following steps:
(1) mixing manganese salt, cobalt salt and nickel salt to obtain mixed salt solution;
(2) mixing ammonia water, alkali liquor, an additive and the mixed salt solution obtained in the step (1) to obtain a raw material solution;
(3) heating and stirring the raw material solution obtained in the step (2), and controlling the pH value to obtain a precipitate;
(4) and (4) washing and drying the precipitate obtained in the step (3) in sequence to obtain the manganese-rich hydroxide precursor.
2. The preparation method according to claim 1, wherein the molar ratio of manganese, cobalt and nickel in the mixed salt solution in the step (1) is Mn: Co: Ni ═ x: y (1-x-y), wherein x is 0.4. ltoreq. x.ltoreq.1, and y is 0. ltoreq. y.ltoreq.0.3;
preferably, the mixed salt solution of the step (1) has a mixed salt concentration of 1-2 mol/L.
3. The method according to claim 1 or 2, wherein the concentration of the ammonia water in the step (2) is 5 to 25% by mass;
preferably, the alkali liquor in the step (2) is alkali metal hydroxide solution;
preferably, the alkali metal hydroxide comprises any one of sodium hydroxide, potassium hydroxide or lithium hydroxide or a combination of at least two thereof;
preferably, the concentration of the alkali metal hydroxide solution is 4 to 8 mol/L.
4. The method according to any one of claims 1 to 3, wherein the additive of step (2) comprises any one or a combination of at least two of sodium hypophosphite, sodium borohydride, formaldehyde, lithium aluminum hydride, lithium borohydride, nickel borohydride or sodium sulfite;
preferably, the additives in the step (2) are prepared into a solution and then mixed;
preferably, the concentration of the additive in the step (2) is 0.01-5 mol/L.
5. The production method according to any one of claims 1 to 4, wherein the concentration of ammonia in the raw material solution in the step (2) is 0.02 to 1 mol/L;
preferably, the concentration of the additive in the raw material solution in the step (2) is 0.001-2 mol/L.
6. The method according to any one of claims 1 to 5, wherein the temperature of the heating and stirring in the step (3) is 50 to 70 ℃;
preferably, the rotation speed of the heating and stirring in the step (3) is 300-;
preferably, the heating and stirring time of the step (3) is 6-48 h;
preferably, the pH of step (3) is 9-12;
preferably, the precipitate obtained in step (3) has a particle size in the range of 3 to 10 μm.
7. The method according to any one of claims 1 to 6, wherein the washed detergent of step (4) comprises water;
preferably, the temperature for drying in step (4) is 90-120 ℃.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) mixing manganese salt, cobalt salt and nickel salt to obtain mixed salt solution; the concentration of the mixed salt is 1-2mol/L, the molar ratio of manganese, cobalt and nickel in the mixed salt solution is Mn, Co, Ni and x, y and (1-x-y), wherein x is more than or equal to 0.4 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.3;
(2) mixing ammonia water, alkali liquor, an additive and the mixed salt solution obtained in the step (1) to obtain a raw material solution; the concentration of ammonia in the raw material solution is 0.02-1mol/L, and the concentration of the additive is 0.001-2 mol/L;
(3) heating and stirring the raw material solution obtained in the step (2), and controlling the pH to be 9-12 to obtain a precipitate with the particle size range of 3-10 mu m; the heating and stirring temperature is 50-70 ℃, the time is 6-48h, and the stirring speed is 300-;
(4) washing and drying the precipitate obtained in the step (3) to obtain the manganese-rich hydroxide precursor; the washing detergent comprises water, and the drying temperature is 90-120 ℃;
the mass percentage concentration of the ammonia water in the step (2) is 5-25%; the alkali liquor is an alkali metal hydroxide solution, the alkali metal hydroxide comprises any one or the combination of at least two of sodium hydroxide, potassium hydroxide or lithium hydroxide, and the concentration of the alkali metal hydroxide is 4-8 mol/L;
and (3) the additive in the step (2) comprises any one or combination of at least two of sodium hypophosphite, sodium borohydride, formaldehyde, lithium borohydride, nickel borohydride and sodium sulfite, and the additive is prepared into a solution to be mixed, wherein the concentration of the solution is 0.01-5 mol/L.
9. A manganese-rich hydroxide precursor obtained by the preparation method according to any one of claims 1 to 8, wherein the chemical formula of the manganese-rich hydroxide precursor is MnxCoyNi1-x-y(OH)2Wherein x is more than or equal to 0.4, and y is less than or equal to 0.3.
10. Use of the manganese-rich hydroxide precursor according to claim 9 in a lithium ion battery.
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