CN114988479A - Manganese-containing material and preparation method thereof, and lithium manganate and preparation method and application thereof - Google Patents
Manganese-containing material and preparation method thereof, and lithium manganate and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a manganese-containing material and a preparation method thereof, and lithium manganate and a preparation method and application thereof, wherein the manganese-containing material has the following characteristic peaks in an XRD (X-ray diffraction) spectrum of a 2 theta diffraction angle: characteristic peak F1: 21-22 °, characteristic peak F2: 24-25 °, characteristic peak F3: 30-31 °, characteristic peak F4: 31-32 °, characteristic peak F5: 33-35 ° characteristic peak F6: 51-53 degrees, and the ratio of the characteristic peak F1 to the characteristic peak F2 is more than 0 (F1/F2) and less than or equal to 5. According to the manganese-containing material, the lithium element and the manganese element are uniformly distributed, and the structure is stable.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a manganese-containing material and a preparation method thereof, and lithium manganate and a preparation method and application thereof.
Background
In the prior art, a manganese source raw material and a lithium source raw material are generally mixed and sintered at high temperature to prepare lithium manganate, and in the process, the mixing needs mixing and mixing operation, the mixing is a key ring in the traditional production process of lithium manganate materials, and not only is an independent quantitative value required for each material, but also the proportion of the materials put into the lithium manganate materials must be correct. However, in the burdening process, due to water absorption of materials, operation of personnel or fluctuation of equipment, errors of lithium proportioning are easily caused, the consistency of batches is reduced, and even the electrical property of lithium manganate is reduced.
In the mixing process, a layering phenomenon is easily generated due to a large density difference between the lithium source and the manganese source. And due to solid-phase mixing, the material mixing is not uniform, and the consistency of the product lithium manganate is poor.
In the high-temperature sintering process, because a phase interface between a manganese source and a lithium source exists, and the solid-phase diffusion speed of lithium ions is low at the phase interface, the lithium ions in the lithium source are difficult to permeate into the particles of the manganese source, so that the lithium ion concentration on the surface of the particles is inconsistent with that in the particles, even the core part of the particles is lack of lithium, and the electrical property of the prepared lithium manganate is poor.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the manganese-containing material is provided, and the lithium element and the manganese element are uniformly distributed and have stable structures.
In order to achieve the purpose, the invention adopts the following technical scheme:
a manganese-containing material having the following characteristic peaks in an XRD pattern at 2-theta diffraction angles: characteristic peak F1: 21-22 °, characteristic peak F2: 24-25 °, characteristic peak F3: 30-31 °, characteristic peak F4: 31-32 °, characteristic peak F5: 33-35 ° characteristic peak F6: 51-53 degrees, and the ratio of the characteristic peak F1 to the characteristic peak F2 is more than 0 (F1/F2) and less than or equal to 5. The peak intensity of the characteristic peak F1 can represent the content of lithium element in the crystal, and the peak intensity of the characteristic peak F2 can represent the content of manganese element in the crystal.
Preferably, the manganese-containing material has the chemical formula of Li x Mn y A z (CO 3 ) m B n Wherein x is more than or equal to 0.001 and less than 2, y is more than or equal to 0.001 and less than 1,0≤z＜y，0<m is less than or equal to 1, n is less than or equal to 0 and less than or equal to 2, A is cation, the cation comprises one or more atoms of Na, K, Ca, Mg, Sr, Y, Ti, Zr, Nb, Al, Sb, Fe, Co, Ni, Cu and Zn, one or more electrons are lost to achieve ions of stable structure, B is anion, and the anion comprises F - 、Cl - 、OH - 、C 2 O 4 2- 、SO 4 2- 、O 2- 、S 2- 、PO 4 3- 、P 2 O 7 4- 、P 3 O 10 5- One or more of (a).
Preferably, the mass fraction of lithium in the manganese-containing material is 0.01-18%, and the mass fraction ratio of lithium to manganese in the manganese-containing material is 0.1-200%.
Preferably, the particle diameter D50 of the manganese-containing material is 2-15 μm.
The second purpose of the invention is: aiming at the defects of the prior art, the preparation method of the manganese-containing material is provided, has simple operation and good controllability, and can be used for batch production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of preparing a manganese-containing material, comprising the steps of:
step S1, mixing a manganese salt solution and a lithium salt solution to obtain a metal salt mixed solution;
step S2, mixing and stirring a precipitator and an auxiliary agent under an inert atmosphere, adding a metal salt mixed solution, and carrying out a coprecipitation reaction to obtain a precipitation product;
and step S3, aging, filtering, washing and drying the precipitation product to obtain the manganese-containing material.
Preferably, the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the solute in the precipitation solution and the solute in the auxiliary agent is 150-200: 50-120: 120-250: 0.1-12.
Preferably, the step S1 or the step S2 further comprises a doping liquid, and the weight part of the non-volatile matter in the doping liquid is 1-300.
The third purpose of the invention is that: aiming at the defects of the prior art, the preparation method of the lithium manganate is provided, has simple steps and can be used for batch production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of lithium manganate is provided, wherein the manganese-containing material is heated to 500-850 ℃ and sintered to obtain the lithium manganate.
The fourth purpose of the invention is that: aiming at the defects of the prior art, the lithium manganate has good uniformity, uniform distribution of lithium element and manganese element and good electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
lithium manganate is obtained by the preparation method of lithium manganate.
The fifth purpose of the invention is that: aiming at the defects of the prior art, the positive plate is provided, and has good stability and chemical properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
a positive plate comprises the lithium manganate.
The sixth purpose of the invention is that: aiming at the defects of the prior art, the lithium ion battery is provided, and has good electrochemical performance and stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery comprises the positive plate.
Compared with the prior art, the invention has the beneficial effects that: according to the manganese-containing material, the lithium element and the manganese element are uniformly distributed, and the structure is stable.
Drawings
Figure 1 is an XRD pattern of a manganese-containing material of the present invention.
Fig. 2 is an SEM image of a manganese-containing material of the present invention.
Figure 3 is an XRD pattern of the product of the manganese-containing material of the present invention after heating at 550 ℃.
Figure 4 is an XRD pattern of the product of the manganese-containing material of the present invention after heating at 760 deg.c.
Fig. 5 is an SEM image of the product of the manganese-containing material of the present invention after heating at 760 ℃.
Fig. 6 is an SEM image of a manganese-containing material of the present invention after doping with aluminum.
Fig. 7 is an SEM image of the product of the aluminum doped manganese containing material of the present invention after heating at 800 c.
Detailed Description
1. A manganese-containing material having the following characteristic peaks in an XRD pattern at 2-theta diffraction angles: characteristic peak F1: 21-22 °, characteristic peak F2: 24-25 °, characteristic peak F3: 30-31 °, characteristic peak F4: 31-32 °, characteristic peak F5: 33-35 °, characteristic peak F6: 51-53 degrees, and the ratio of the characteristic peak F1 to the characteristic peak F2 is more than 0 (F1/F2) and less than or equal to 5. The peak intensity of the characteristic peak F1 can represent the content of lithium element in the crystal, and the peak intensity of the characteristic peak F2 can represent the content of manganese element in the crystal.
Preferably, the manganese-containing material has the chemical formula of Li x Mn y A z (CO 3 ) m B n Wherein x is more than or equal to 0.001 and less than 2, y is more than or equal to 0.001 and less than 1, z is more than or equal to 0 and less than y, 0<m is less than or equal to 1, n is less than or equal to 0 and less than or equal to 2, A is cation, the cation comprises one or more atoms of Na, K, Ca, Mg, Sr, Y, Ti, Zr, Nb, Al, Sb, Fe, Co, Ni, Cu and Zn, one or more electrons are lost to achieve ions of stable structure, B is anion, and the anion comprises F - 、Cl - 、OH - 、C 2 O 4 2- 、SO 4 2- 、O 2- 、S 2- 、PO 4 3- 、P 2 O 7 4-- 、P 3 O 10 5- One or more of (a).
Preferably, the mass fraction of lithium in the manganese-containing material is 0.01-18%, and the mass fraction ratio of lithium to manganese in the manganese-containing material is 0.1-200%.
Preferably, the particle diameter D50 of the manganese-containing material is 2-15 μm.
2. The preparation method of the manganese-containing material is simple to operate, good in controllability and capable of realizing batch production.
A method of preparing a manganese-containing material, comprising the steps of:
step S1, mixing a manganese salt solution and a lithium salt solution to obtain a metal salt mixed solution;
step S2, mixing and stirring a precipitator and an auxiliary agent under an inert atmosphere, adding a metal salt mixed solution, and carrying out a coprecipitation reaction to obtain a precipitation product;
and step S3, aging, filtering, washing and drying the precipitation product to obtain the manganese-containing material.
The manganese-containing material disclosed by the invention is formed into a microreactor by adopting a high-molecular surfactant under the condition of an inert atmosphere, and the adsorption characteristic of manganese precipitate is utilized to regulate and control occlusion and entrapment by controlling the supersaturation degree, so that the mixed crystal precipitation of lithium and manganese is realized, the product has the advantages of good crystallinity, stable composition, good consistency and high purity, is suitable for large-scale production, and avoids ammonia nitrogen waste gas in the sintering process.
The preparation method realizes the coprecipitation of lithium and manganese, and reduces the subsequent batching process and lithium mixing process. The equipment such as an inclined mixer, a double-cone spiral mixer, a ball mill mixer, a high-speed mixer and the like is not needed, and the cost is reduced. The lithium proportion error caused by water absorption of materials, operation of personnel or fluctuation of equipment is avoided, and the consistency of lithium manganate materials in different batches is improved.
Preferably, the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the solute in the precipitation solution and the solute in the auxiliary agent is 150-200: 50-120: 120-250: 0.1-12.
Preferably, the step S1 or S2 further includes a doping liquid, and the weight portion of the non-volatile matter in the doping liquid is 1-300. When a doping liquid is added in step S1, adding the doping liquid to the metal salt mixed liquid; when the doping liquid is added in step S2, the doping liquid is added before, after, or at the same time as the addition of the metal salt mixed liquid.
Wherein the manganese salt is selected from one or more of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate, manganese citrate and manganese sulfite, preferably manganese sulfate.
Wherein the lithium salt is selected from one or more of lithium sulfate, lithium chloride, lithium nitrate, lithium sulfite, lithium chlorate, lithium perchlorate, lithium bromide, lithium bromate, lithium iodide, lithium thiocyanate, lithium nitrite, lithium formate, lithium acetate, lithium citrate and lithium oxalate, and lithium sulfate is preferred.
The doping liquid is obtained by dispersing ionic compound in water, wherein the cation of the ionic compound can be one or more of Na, K, Ca, Mg, Sr, Y, Ti, Zr, Nb, Al, Sb, Fe, Co, Ni, Cu and Zn, and the ion or NH of which one or more atoms lose one or more electrons to achieve a stable structure 4 + The anion may be F - 、Cl - 、OH - 、NO 3 - 、C 2 O 4 2- 、SO 4 2- 、O 2- 、S 2- 、PO 4 3- 、P 2 O 7 4- 、P 3 O 10 5- One or more of (a).
The precipitant is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide and ammonia water, preferably sodium carbonate.
The auxiliary agent is one of cationic surfactant, anionic surfactant, nonionic surfactant, combination of cationic surfactant and nonionic surfactant, and combination of anionic surfactant and nonionic surfactant. Preferably one or more of fatty alcohol-polyoxyethylene ether, fatty acid-polyoxyethylene ester, alkyl polyglycoside, alkylolamide, ethoxylated sorbitan fatty acid ester, and the like, and more preferably fatty alcohol-polyoxyethylene ether.
3. The preparation method of the lithium manganate has simple steps and can be used for batch production.
A preparation method of lithium manganate is provided, wherein the manganese-containing material is heated to 500-850 ℃ and sintered to obtain the lithium manganate.
The traditional sintering temperature is high, and the sintering time is long at 800-900 ℃ for 10-20 hours. In the sintering process at 500-850 ℃, lithium ions are uniformly distributed in the manganese-containing material, so that the lithium manganate material with uniformly distributed lithium is obtained, and the electrical property of lithium manganate is improved; in the sintering process, because the lithium ions are uniformly distributed in the manganese-containing material and no phase interface exists, the mass transfer resistance of the lithium ions is reduced, the reaction temperature and the reaction time can be reduced, the energy consumption is reduced, and the cost is reduced.
4. The lithium manganate has good homogeneity, homogeneous distribution of lithium element and manganese element and good electrochemical performance.
Lithium manganate obtained by the preparation method of lithium manganate.
5. The positive plate has good stability and chemical performance.
A positive plate comprises the lithium manganate.
6. A lithium ion battery has good electrochemical performance and stability.
A lithium ion battery comprises the positive plate. Specifically, the lithium ion battery comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, wherein the positive plate and the negative plate are separated by the diaphragm, and the shell is used for mounting the positive plate, the negative plate, the diaphragm and the electrolyte. The positive plate is the positive plate.
The negative plate comprises a negative current collector and a negative active material layer arranged on the surface of the negative current collector, wherein the negative active material layer comprises a negative active material, and the negative active material can be one or more of graphite, soft carbon, hard carbon, carbon fiber, mesocarbon microbeads, silicon-based materials, tin-based materials, lithium titanate or other metals capable of forming an alloy with lithium. Wherein, the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite; the silicon-based material can be one or more selected from simple substance silicon, silicon-oxygen compound, silicon-carbon compound and silicon alloy; the tin-based material can be one or more selected from simple substance tin, tin oxide compound and tin alloy. The negative electrode current collector is generally a structure or a part for collecting current, and the negative electrode current collector may be any material suitable for use as a negative electrode current collector of a lithium ion battery in the art, for example, the negative electrode current collector may include, but is not limited to, a metal foil, and the like, and more specifically, may include, but is not limited to, a copper foil, and the like.
The lithium ion battery also comprises electrolyte, and the electrolyte comprises an organic solvent, electrolyte lithium salt and an additive. Wherein the electrolyte lithium salt may be LiPF used in a high-temperature electrolyte 6 And/or LiBOB; or LiBF used in low-temperature electrolyte 4 、LiBOB、LiPF 6 At least one of; or LiBF used in anti-overcharge electrolyte 4 、LiBOB、LiPF 6 At least one of LiTFSI; may also be LiClO 4 、LiAsF 6 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) 2 At least one of (a). And the organic solvent may be a cyclic carbonate including PC, EC; or chain carbonates including DFC, DMC, or EMC; and also carboxylic acid esters including MF, MA, EA, MP, etc. And additives include, but are not limited to, film forming additives, conductive additives, flame retardant additives, overcharge prevention additives, controlling H in electrolytes 2 At least one of additives of O and HF content, additives for improving low temperature performance, and multifunctional additives.
Preferably, the material of the shell is one of stainless steel and an aluminum plastic film. More preferably, the housing is an aluminum plastic film.
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
Example 1
1. A method of preparing a manganese-containing material, comprising the steps of:
step S1, weighing 171.68g of manganese sulfate monohydrate, adding water to dissolve, diluting to constant volume to 1L, and preparing 1mol/L MnSO 4 The solution is manganese salt solution; 129.25g of lithium sulfate monohydrate is weighed, dissolved by adding water, diluted to 1L to obtain 1mol/L Li 2 SO 4 The solution is a lithium salt solution;
mixing 100mL of the manganese salt solution and 60mL of the lithium salt solution to obtain a metal salt mixed solution;
step S2, weighing 107.60g sodium carbonate, adding water to dissolveDissolving, diluting to constant volume of 1L, and preparing 1mol/L Na 2 CO 3 The solution is a precipitant; weighing 0.064g of fatty alcohol-polyoxyethylene ether (AEO9) as an auxiliary agent;
under the inert atmosphere, adding 160mL of precipitator and the auxiliary agent into a reaction kettle for mixing and stirring, adding the metal salt mixed solution and the doping solution, and carrying out coprecipitation reaction to obtain a precipitation product; wherein the temperature of the reaction kettle is 70 ℃ under the condition of N 2 Under the protective atmosphere, the rotating speed of a stirrer is 1000rpm, the feeding speed is 0.1mL/min, and a metal salt mixed solution M is added to separate out light pink sediment;
and step S3, aging the precipitate at 70 ℃ for 12h, performing suction filtration, separating a filter cake and filtrate, washing the filter cake with deionized water at 70 ℃ for 4 times, and drying in a 120 ℃ oven to constant weight to obtain the manganese-containing material, wherein lithium and manganese are uniformly distributed in particles.
The XRD pattern of the material is shown in figure 1, wherein the characteristic peak F1/F2 is 0.477. The SEM picture is shown in figure 2.
Wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the solute in the precipitation solution and the solute in the auxiliary agent is 169:79:171: 0.64.
Preparing a lithium manganate material: heating the manganese-containing material to a sintering temperature of 760 ℃ for 10h to obtain lithium manganate, wherein fig. 3 and 4 are XRD diagrams of products of the manganese-containing material heated at 550 ℃ and 760 ℃, respectively, and fig. 5 is an SEM diagram of the products of the manganese-containing material heated at 760 ℃.
2. Preparing a positive plate: mixing the prepared lithium manganate, conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97: 1.5: 1.5, uniformly mixing to prepare lithium ion battery anode slurry with certain viscosity, coating the slurry on a current collector aluminum foil, drying at 85 ℃, and then carrying out cold pressing; then trimming, cutting into pieces, slitting, drying for 4 hours at 110 ℃ under the vacuum condition after slitting, and welding the tabs to prepare the lithium ion battery positive plate.
3. Preparing a negative plate: graphite, conductive agent superconducting carbon (Super-P), thickening agent carboxymethyl cellulose sodium (CMC) and binder Styrene Butadiene Rubber (SBR) are mixed according to a mass ratio of 96: 2.0: 1.0: 1.0, preparing slurry, coating the slurry on a current collector copper foil, drying at 85 ℃, cutting edges, cutting pieces, dividing strips, drying for 4 hours at 110 ℃ under a vacuum condition after dividing the strips, and welding lugs to prepare the lithium ion battery negative plate.
4. Preparing an electrolyte: mixing lithium hexafluorophosphate (LiPF) 6 ) Dissolving the mixture in a mixed solvent composed of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) (the mass ratio of the three is 1: 2: 1) to obtain the electrolyte with the concentration of 1 mol/L.
5. Preparing a lithium ion battery: winding the prepared positive plate, the diaphragm and the negative plate into a battery cell, wherein the oily diaphragm is positioned between the positive plate and the negative plate, the positive electrode is led out by spot welding of an aluminum tab, and the negative electrode is led out by spot welding of a nickel tab; and then placing the battery core in an aluminum-plastic packaging bag, injecting the electrolyte, and carrying out processes such as packaging, formation, capacity and the like to prepare the lithium ion battery.
Example 2
A preparation method of a manganese-containing material doped with Al element comprises the following steps:
step S1, weighing 171.68g of manganese sulfate monohydrate, adding water to dissolve, diluting to constant volume to 1L, and preparing 1mol/L MnSO 4 The solution is manganese salt solution; 129.25g of lithium sulfate monohydrate is weighed, dissolved by adding water, diluted to 1L to obtain 1mol/L Li 2 SO 4 The solution is a lithium salt solution;
mixing 100mL of the manganese salt solution and 60mL of the lithium salt solution to obtain a metal salt mixed solution;
step S2, weighing 336.45g of aluminum sulfate octadecahydrate, adding water to dissolve, diluting to constant volume of 1L, 0.5mol/L Al 2 (SO 4 ) 3 Taking 10mL of the solution as doping liquid; 107.60g of sodium carbonate is weighed, water is added for dissolution, the solution is diluted to a constant volume of 1L, and 1mol/LNa is prepared 2 CO 3 The solution is a precipitant; weighing 0.064g of fatty alcohol-polyoxyethylene ether (AEO9) as an auxiliary agent;
under inert atmosphere, adding 175mL of precipitator and the auxiliary agent into a reaction kettle for mixing and stirring, adding the metal salt mixed solution and the doping solution, and carrying out coprecipitation reaction to obtain a precipitation product; wherein the temperature of the reaction kettle is 70 ℃ belowN 2 Under the protective atmosphere, the rotating speed of a stirrer is 1000rpm, the feeding speed is 0.1mL/min, and the metal salt mixed solution M is added to separate out light pink sediment;
and step S3, aging the precipitate at 70 ℃ for 12h, performing suction filtration, separating a filter cake and filtrate, washing the filter cake with deionized water at 70 ℃ for 4 times, drying in a 120 ℃ oven to constant weight to obtain the manganese-containing material, wherein lithium, manganese and aluminum are uniformly distributed in particles, and an SEM picture is shown in figure 6.
Wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping liquid, the solute in the precipitation liquid and the solute in the auxiliary agent is 169:79:31:186: 0.64.
Preparing a lithium manganate material: and (3) taking the manganese-containing material, placing the manganese-containing material in a muffle furnace, and sintering the manganese-containing material for 3h at 800 ℃ to obtain black aluminum-doped lithium manganate powder, wherein the SEM image of the black aluminum-doped lithium manganate powder is shown in an attached figure 7.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 2 is that: wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent is 169:79:16:179: 0.64.
The rest is the same as embodiment 2, and the description is omitted here.
Example 4
The difference from example 2 is that: wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent is 169:79:5:174: 0.64.
The rest is the same as embodiment 2, and the description is omitted here.
Example 5
The difference from example 2 is that: wherein the nonvolatile matter in the doping liquid is yttrium sulfate octahydrate. The weight ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent is 169:80:1:172: 0.64.
The rest is the same as embodiment 2, and the description is omitted here.
Example 6
The differences from example 5 are: wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent is 170:79:2:173: 0.64.
The rest is the same as embodiment 2, and the description is omitted here.
Example 7
The difference from example 2 is that: wherein the non-volatile matter in the doping liquid is anhydrous lanthanum sulfate. Wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent is 169:79:1:172: 0.78.
The rest is the same as embodiment 2, and the description is omitted here.
Example 8
The difference from example 7 is that: wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent is 169:79:2:173: 0.78.
The rest is the same as embodiment 2, and the description is omitted here.
Example 9
The difference from example 2 is that: wherein the non-volatile matter in the doping liquid is aluminum sulfate octadecahydrate and yttrium sulfate octahydrate, and the weight part ratio of the aluminum sulfate octadecahydrate to the yttrium sulfate octahydrate is 50: 1. Wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent is 169:79:5.1:174: 0.64.
The rest is the same as embodiment 2, and the description is omitted here.
Example 10
The difference from example 9 is that: wherein the weight part ratio of the aluminum sulfate octadecahydrate to the yttrium sulfate octadecahydrate is 5: 1. Wherein the weight part ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the nonvolatile matter in the doping liquid, the solute in the precipitation liquid and the solute in the auxiliary agent is 169:79:6.2:175: 0.94.
The rest is the same as embodiment 2, and the description is omitted here.
Example 11
Preparation method of manganese-containing material doped with Ni element
1. Preparing a metal salt mixed solution M containing doped ions: 34.34g of manganese sulfate monohydrate, 15.51g of lithium sulfate monohydrate and 0.21g of nickel sulfate hexahydrate are weighed, 320g of water is added for dissolution, and the mixture is magnetically stirred uniformly to obtain a metal salt mixed solution M.
2. Preparing a precipitator P: 35.51g of sodium carbonate is weighed, 320g of water is added for dissolution, and the mixture is stirred evenly by magnetic force to obtain the precipitator P.
3. 0.13g of fatty alcohol-polyoxyethylene ether (AEO9) as an auxiliary agent Z is weighed.
4. And (3) adding a precipitator P and an auxiliary agent Z into the reaction kettle in advance, and uniformly stirring. The temperature of the reaction kettle is 65 ℃, the rotating speed of a stirrer is 900rpm under the protection atmosphere of N2, the feeding speed is 0.2mL/min, and the metal salt mixed solution M is slowly added into the liquid containing the auxiliary agent Z and the precipitator P to separate out light green precipitates.
5. After all the additions were complete, the slurry was stirred and aged at 70 ℃ for 12 h.
6. And (4) carrying out suction filtration on the filter cake, and separating the filter cake from the filtrate.
7. The filter cake was washed 3 times with deionized water at 70 ℃.
8. Drying the mixture in an oven at 120 ℃ to constant weight to obtain the Ni-doped manganese-containing material.
9. And (3) putting the manganese-containing material into a muffle furnace, and sintering for 3h at 810 ℃ to obtain nickel-doped lithium manganate powder.
The rest is the same as embodiment 2, and the description is omitted here.
Example 12
A preparation method of a Mg-doped manganese-containing material comprises the following steps:
1. preparing a metal salt mixed solution M containing doped ions: 42.92g of manganese sulfate monohydrate, 19.39g of lithium sulfate monohydrate and 0.25g of magnesium sulfate heptahydrate are weighed, 480g of water is added for dissolution, and the mixture is stirred uniformly by magnetic force to obtain a metal salt mixed solution M.
2. Preparing a precipitator P: 44.39g of sodium carbonate is weighed, 480g of water is added for dissolution, and the mixture is stirred evenly by magnetic force to obtain a precipitator P.
3. 0.16g of fatty alcohol-polyoxyethylene ether (AEO9) as an auxiliary Z.
4. And (3) adding a precipitator P and an auxiliary agent Z into the reaction kettle in advance, and uniformly stirring. The temperature of the reaction kettle is 70 ℃, the rotating speed of a stirrer is 950rpm under the protection atmosphere of N2, the feeding speed is 0.3mL/min, and the metal salt mixed solution M is slowly added into the liquid containing the auxiliary agent Z and the precipitator P to separate out light pink precipitates.
5. After the complete addition, the slurry was stirred further and aged at 65 ℃ for 12 h.
6. And (4) carrying out suction filtration on the filter cake, and separating the filter cake from the filtrate.
7. The filter cake was washed 3 times with deionized water at 70 ℃.
8. Drying the mixture in an oven at 120 ℃ to constant weight to obtain the Mg-doped manganese-containing material.
9. And (3) putting the manganese-containing material into a muffle furnace, and sintering at 820 ℃ for 3h to obtain magnesium-doped lithium manganate powder.
The rest is the same as embodiment 2, and the description is omitted here.
Example 13
Doped with C 2 O 4 2- The preparation method of the manganese-containing material comprises the following steps:
1. preparing a metal salt mixed solution M containing doped ions: 34.34g of manganese sulfate monohydrate and 15.51g of lithium sulfate monohydrate are weighed, 320g of water is added for dissolution, and the mixture is magnetically stirred uniformly to obtain a metal salt mixed solution M.
2. Preparing a precipitator P: 28.80g of ammonium carbonate is weighed, 160g of water is added for dissolution, and the mixture is stirred uniformly by magnetic force to obtain a precipitator P.
3. Preparing a doping liquid D: 2.84g of ammonium oxalate monohydrate was weighed and dissolved in 160g of water.
4. 0.13g of fatty alcohol-polyoxyethylene ether (AEO9) as an auxiliary agent Z is weighed.
5. And (3) adding a precipitator P and an auxiliary agent Z into the reaction kettle in advance, and uniformly stirring. The temperature of the reaction kettle is 60 ℃, the rotating speed of a stirrer is 900rpm under the protective atmosphere of N2, the feeding speed of a metal salt mixed solution M is 0.2mL/min, the feeding speed of a doping solution D is 0.1mL/min, the metal salt mixed solution M and the doping solution D are added into a liquid containing an auxiliary agent Z and a precipitator P together, and light pink precipitates are separated out.
6. After all the addition was complete, the slurry was stirred and aged at 60 ℃ for 12 h.
7. And (4) carrying out suction filtration on the filter cake, and separating the filter cake from the filtrate.
8. The filter cake was washed 3 times with deionized water at 70 ℃.
9. Drying in an oven at 120 deg.C to constant weight to obtain a product doped with C 2 O 4 2- The manganese-containing material of (1).
The rest is the same as embodiment 2, and the description is omitted here.
Example 14
Doped with PO 4 3- The preparation method of the manganese-containing material comprises the following steps:
1. preparing a metal salt mixed solution M containing doped ions: 171.68g of manganese sulfate monohydrate and 77.55g of lithium sulfate monohydrate are weighed, 1600g of water is added for dissolution, and the mixture is stirred uniformly by magnetic force to obtain a metal salt mixed solution M.
2. Preparing a precipitator P: 161.4g of sodium carbonate is weighed, 800g of water is added for dissolution, and the mixture is stirred uniformly by magnetic force to obtain a precipitator P.
3. Preparing a doping liquid D: 19.45g of trisodium phosphate dodecahydrate is weighed and dissolved by adding 800g of water.
4. And (3) 1.28g of auxiliary agent Z, namely fatty alcohol-polyoxyethylene ether (AEO 9).
5. Adding a precipitator P and an auxiliary agent Z into the reaction kettle in advance, and stirring uniformly. The temperature of the reaction kettle is 70 ℃ under N 2 Under the protective atmosphere, the rotating speed of the stirrer is 500rpm, the feeding speed of the metal salt mixed solution M is 1mL/min, the feeding speed of the doping solution D is 0.5mL/min, and the metal salt mixed solution M and the doping solution D are added into the liquid containing the auxiliary agent Z and the precipitator P together to separate out light pink precipitates.
6. After all the additions were complete, the slurry was stirred and aged at 70 ℃ for 12 h.
7. The slurry was centrifuged to separate the filter cake from the filtrate.
8. The filter cake was washed 2 times with deionized water at 70 ℃.
9. Drying in an oven at 120 deg.C to constant weight to obtain a product doped with PO 4 3- The manganese-containing material of (1).
The rest is the same as embodiment 2, and the description is omitted here.
Comparative example 1
351.25g of electrolytic manganese dioxide and 37.13g of lithium carbonate are weighed, ball-milled and mixed evenly, placed in a muffle furnace at 800 ℃ and sintered for 20 hours to obtain the conventional lithium manganate.
And (3) performance testing: the lithium ion batteries prepared in the above examples 1 to 14 and comparative example 1 were subjected to performance tests, and the test results are recorded in table 1.
Capacity retention rate test: charging the lithium ion secondary battery to 4.25V at a constant current of 1C at 25 ℃, then charging to 0.05C at a constant voltage of 4.25V, standing for 5min, and then discharging to 2.8V at a constant current of 1C, wherein the process is a charge-discharge cycle process, and the discharge capacity of the time is the discharge capacity of the first cycle. The lithium ion secondary battery was subjected to 400-cycle charge/discharge tests in accordance with the above-described method, and the discharge capacity per one cycle was recorded. The cycle capacity retention (%) was 400 cycles of discharge capacity/first cycle of discharge capacity × 100%.
TABLE 1
Compared with the comparative example, the manganese-containing material prepared by the invention is applied to the lithium ion battery, and the prepared lithium ion battery has higher capacity and better capacity retention rate, still maintains 83% of capacity retention rate after 400 charge-discharge cycles under the conventional condition, and has good performance.
The comparison of the examples 1 to 14 shows that when the Y is doped, the ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the non-volatile matter in the doping solution, the solute in the precipitation solution and the solute in the auxiliary agent in parts by weight is 170:79:2:173:0.64, the prepared lithium ion battery has better cycle performance, and the capacity retention rate is as high as 95%. From the comparison of examples 1 to 14 with comparative example 1, it is possible to improve the cycle performance of the materials by doping with anions or cations.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (11)
1. A manganese-containing material characterized by having the following characteristic peaks in an XRD pattern of a copper target K α 1 at 2 θ diffraction angles: characteristic peak F1: 21-22 °, characteristic peak F2: 24-25 °, characteristic peak F3: 30-31 °, characteristic peak F4: 31-32 °, characteristic peak F5: 33-35 ° characteristic peak F6: 51-53 degrees, and the ratio of the characteristic peak F1 to the characteristic peak F2 is more than 0 (F1/F2) and less than or equal to 5.
2. The manganese-containing material of claim 1, wherein the manganese-containing material has the formula Li x Mn y A z (CO 3 ) m B n Wherein x is more than or equal to 0.001 and less than 2, y is more than or equal to 0.001 and less than 1, z is more than or equal to 0 and less than y, 0<m is less than or equal to 1, n is less than or equal to 0 and less than or equal to 2, A is cation, the cation comprises one or more of Na, K, Ca, Mg, Sr, Y, Ti, Zr, Nb, Al, Sb, Fe, Co, Ni, Cu and Zn, one or more of atoms lose one or more electrons to achieve the ion of stable structure, B is anion, and the anion comprises F - 、Cl - 、OH - 、C 2 O 4 2- 、SO 4 2- 、O 2- 、S 2- 、PO 4 3- 、P 2 O 7 4- 、P 3 O 10 5- One or more of (a).
3. The manganese-containing material according to claim 1, wherein the mass fraction of lithium in the manganese-containing material is 0.01 to 18%, and the mass fraction ratio of lithium to manganese in the manganese-containing material is 0.1 to 200%.
4. The manganese-containing material according to claim 1, wherein the particle diameter D50 of the manganese-containing material is 2 to 15 μm.
5. A method of producing a manganese-containing material according to any one of claims 1 to 4, comprising the steps of:
step S1, mixing a manganese salt solution and a lithium salt solution to obtain a metal salt mixed solution;
step S2, mixing and stirring a precipitator and an auxiliary agent under an inert atmosphere, adding a metal salt mixed solution, and carrying out a coprecipitation reaction to obtain a precipitation product;
and step S3, aging, filtering, washing and drying the precipitation product to obtain the manganese-containing material.
6. The method for preparing the manganese-containing material according to claim 5, wherein the weight ratio of the solute in the manganese salt solution, the solute in the lithium salt solution, the solute in the precipitation solution and the solute in the auxiliary agent is 150-200: 50-120: 120-250: 0.1-12.
7. The method of claim 5, further comprising a doping solution in step S1 or S2, wherein the doping solution comprises the non-volatile matter in an amount of 1-300 parts by weight.
8. A method for preparing lithium manganate, characterized in that, the manganese-containing material as described in any of claims 1-4 is heated to 500-850 ℃ and sintered to obtain the product.
9. A lithium manganate obtained by the method for producing lithium manganate according to claim 8.
10. A positive electrode sheet comprising the lithium manganate according to claim 9.
11. A lithium ion battery comprising the positive electrode sheet according to claim 10.
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