CN114988384A - Lithium manganate material, preparation method thereof and secondary battery - Google Patents
Lithium manganate material, preparation method thereof and secondary battery Download PDFInfo
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Abstract
The invention belongs to the technical field of secondary batteries, and particularly relates to a lithium manganate material, a preparation method thereof and a secondary battery, wherein the lithium manganate material has a spinel structure, and an XRD spectrogram of the lithium manganate material has the following characteristic peaks: characteristic peak a: 18 ° -19 °, characteristic peak B: 22-26 °, characteristic peak C: 26-30 °, characteristic peak D: 30-35 ° and characteristic peak E: 36 ° -37 °, characteristic peak F: 43.5-44.5 degrees; and the peak intensity ratio I of the characteristic peak B to the characteristic peak A is greater than or equal to 0 and less than or equal to 0.5. The lithium manganate material has the stable structure, so that the oxidation-reduction reaction of transition metal elements under high potential is inhibited, the structural damage is reduced, the dissolution of Mn elements is reduced, a charge-discharge curve has a plurality of charge-discharge platforms, and an obvious reduction-oxidation peak is formed at the position where a dQ/dV curve chart is 3.2V-3.6V.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a lithium manganate material, a preparation method thereof and a secondary battery.
Background
In the lithium ion battery anode material, because the storage capacity of Mn element is rich and the price is low, the lithium ion battery taking the lithium manganate as the anode has a great application prospect in the field (such as low-speed two-wheel vehicles and energy storage power stations) sensitive to the cost of the battery cell.
However, the lithium manganate has poor structural stability due to the existence of Jahn-Teller effect and the dissolution effect of 3-valent Mn ions, thereby causing poor cycle performance. The technical scheme for improving the cycle performance of lithium manganate in the industry is mainly through an element doping process or a coating process.
In view of the above defects existing in the conventional lithium manganate modification, it is necessary to provide a technical solution for solving the above problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the lithium manganate material is provided, and has good structural stability and cycle performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the lithium manganate material is characterized in that the structure of the lithium manganate material is a spinel structure, and an XRD spectrogram of the lithium manganate material has the following characteristic peaks: characteristic peak a: 18 ° -19 °, characteristic peak B: 22-26 °, characteristic peak C: 26-30 °, characteristic peak D: 30-35 °, characteristic peak E: 36 ° -37 °, characteristic peak F: 43.5-44.5 °; the peak intensity ratio I of the characteristic peak B to the characteristic peak A is more than or equal to 0 and less than or equal to 0.5.
Preferably, the chemical formula of the lithium manganate material is as follows: LiA x Mn (2-x) B y O (4-y) ，0<x<2，0<y<4, A is a metal doping element, and the metal doping element is one or more of Al, Ni, Co, Fe, Ti, Sb, Nb, Y and Ce; b is a non-metal anion, and the non-metal anion is NO 3 - 、Cl - 、F - 、PO 4 3- 、SiO 3 2- One or more than one of them.
Preferably, the charge-discharge cut-off voltage of the lithium manganate material is 4.0-5.0V.
Preferably, the metal doping element accounts for 0.1-20% of the lithium manganate material in parts by weight.
Preferably, the lithium manganate material has a median particle diameter D50 of 3-16 μm and a specific surface area of 0.2-15 square meters per gram.
The second purpose of the invention is: aiming at the defects of the prior art, the preparation method of the lithium manganate material is provided, can be used for batch production and has good controllability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a lithium manganate material comprises the following steps:
step S1, lithium salt, manganese salt and doped metal element salt are mixed according to the chemical formula LiA x Mn (2-x) B y O (4-y) Preparing a mixed solution A with the metal ion concentration of 0.5-4 mol/L according to the molar ratio; preparing a precipitating agent and an anion doping agent into a solution B with the concentration of 0.5-6 mol/L according to the ratio of 1: y; preparing a pH regulator into a solution C with the concentration of 1-6 mol/L; preparing a surfactant into a solution D with the concentration of 0.1-10 g/L;
step S2, adding the solution D into a solvent, stirring, adding the mixed solution A and the solution B, stirring and mixing to obtain a treatment solution;
step S3, adding the solution C into the treatment solution to adjust the pH value, aging, washing, filtering and drying to obtain a lithium manganate precursor;
and step S4, heating, sintering and cooling the lithium manganate precursor to obtain the lithium manganate material.
Preferably, in the step S4, the heating rate is 1-6 ℃/min, the sintering temperature is 400-900 ℃, and the sintering time is 2-20 hours.
Preferably, the pH value in the step S3 is 7-11, and the aging time is 5-10 hours.
Wherein the stirring speed in the step S2 is 800-1200 rpm/min, the stirring time is 40-60 min, and the feeding flow rate of the mixed solution A and the mixed solution B is 10-25 ml/min.
Wherein the anion dopant is one or more of ammonium fluoride, ammonium chloride, sodium chloride, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate; the precipitant is one or more of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate and ammonium bicarbonate.
The third purpose of the invention is: aiming at the defects of the prior art, the secondary battery is provided, and has good service life and performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a secondary battery comprises the lithium manganate material.
The secondary battery has a multi-charge-discharge platform characteristic in a charge-discharge curve during charge-discharge at 3.0-4.2V 0.1C.
Preferably, when the secondary battery is charged and discharged at 3.0-4.2V 0.1C, the charging and discharging platform interval is 4.1V-4.2V, the capacity ratio is 30-38%, the capacity ratio of 4.0V-4.1V is 30-38%, the capacity ratio of 3.85V-4.0V is 26-30%, and the capacity ratio of 3.2V-3.4V is 0-4%.
Preferably, the secondary battery has a capacity of 32-35% in a charge-discharge plateau region of 4.1V-4.2V.
Preferably, the secondary battery has a capacity of 32-35% in a charge-discharge plateau region of 4.0V-4.1V.
Preferably, the secondary battery has a capacity ratio of 27 to 29% in a charge-discharge plateau region of 3.85V to 4.0V.
Preferably, the secondary battery has a capacity ratio of 0-2% in a charge-discharge plateau region of 3.2V-3.4V.
Preferably, the curve of dQ/dV of the secondary battery has a redox peak at a position of 3.2V to 3.6V.
Compared with the prior art, the invention has the beneficial effects that: because the lithium manganate material has the XRD structure and good structural stability, after the lithium manganate material is prepared into a battery, a charge-discharge curve has a plurality of charge-discharge platforms, particularly the discharge platforms exist at a low potential of 3.2V-3.6V, and meanwhile, in a dQ/dV curve graph, an obvious reduction oxidation peak exists at the position of 3.2V-3.6V. Due to the electrochemical property of the lithium manganate under the low potential, the oxidation-reduction reaction of transition metal elements under the high potential is inhibited, the structural damage of the material under the high potential is reduced, and particularly the dissolution of Mn elements caused by the structural damage of the material is reduced, so that the battery prepared from the material has good cycle performance.
Drawings
Fig. 1 is an XRD pattern of example 1 of the present invention and comparative example 1.
Fig. 2 is a particle size distribution diagram of the lithium manganate material of example 1 of the present invention.
Fig. 3 is a graph comparing charge and discharge curves of example 1 of the present invention and comparative example 1 under 0.1C conditions.
FIG. 4 is a graph comparing DQ/DV curves at 4.2V for example 1 of the present invention and comparative example 1.
FIG. 5 is a graph comparing capacity retention under RT1C/1C conditions for example 1 of the present invention and comparative example 1.
Detailed Description
1. The lithium manganate material has good structural stability and cycle performance.
The lithium manganate material is of a spinel structure, and has the following characteristic peaks in an XRD spectrogram under a 2theta diffraction angle: characteristic peak a: 18 ° -19 °, characteristic peak B: 22-26 °, characteristic peak C: 26-30 °, characteristic peak D: 30-35 ° and characteristic peak E: 36 ° -37 °, characteristic peak F: 43.5-44.5 degrees; the peak intensity ratio I of the characteristic peak B to the characteristic peak A is more than or equal to 0 and less than or equal to 0.5.
The conventional commercially available lithium manganate material is of a single spinel lithium manganate structure, and in the process of battery cycle manufacturing, the crystal structure is changed from a cubic crystal system to a tetragonal crystal system, so that thixotropic looseness caused by close contact between positive electrode materials is caused, Li ions are difficult to diffuse, and cycle attenuation is caused. The invention discovers that when the lithium manganate material has the XRD structure, the lithium manganate material has good structural stability. When the lithium manganate material is applied to the anode of a lithium ion battery, the energy density is greatly improved, and the battery has good cycle performance. Characteristic peak A: represents the crystal structure of lithium manganate, and the characteristic peak B: the ratio of B/A is related to the content of the doping elements and is mutually constrained with the content of the doping elements, and when the ratio of the characteristic peak B to the characteristic peak A is more than or equal to 0 and less than or equal to I and less than or equal to 0.5, the prepared material has better structural stability and better cycle performance.
Preferably, the chemical formula of the lithium manganate material is as follows: LiA x Mn (2-x) B y O (4-y) ，0<x<2，0<y<4, A is a metal doping element, and the metal doping element is one or more of Al, Ni, Co, Fe, Ti, Sb, Nb, Y and Ce; b is a non-metal anion, and the non-metal anion is NO 3 - 、Cl - 、F - 、PO 4 3- 、SiO 3 2- One or more than one of them.
The inventor further discovers that the lithium manganate material disclosed by the application has the characteristics that two or more than two crystal structures of lithium manganate and doping elements exist through XRD (X-ray diffraction), and the doping elements and the lithium manganate form LiMn 2 O 4-y A x B y Different phase boundary due to LiMn 2 O 4-y A x B y The problems of capacity attenuation and poor cycle performance of the battery caused by the phase change of the lithium manganese oxide material in the battery cycle process are solved.
Preferably, the metal doping element accounts for 0.1-20% of the lithium manganate material in parts by weight. The metal doping element and the lithium manganate form a stable structure, so that the problems of capacity attenuation and poor cycle performance of the lithium manganate battery caused by the structural change of the lithium manganate due to the over-insertion or over-removal of lithium ions are effectively solved.
Preferably, the charge-discharge cut-off voltage of the lithium manganate material is 4.0-5.0V. The modified lithium manganate has higher cut-off voltage and can be suitable for high-voltage environment.
Preferably, the metal doping element accounts for 0.1-20% of the lithium manganate material in parts by weight. The metal doping elements account for 0.1%, 1%, 3%, 5%, 8%, 10%, 15% and 20% of the lithium manganate material.
Preferably, the lithium manganate material has a median particle diameter D50 of 3-16 μm and a specific surface area of 0.2-15 square meters per gram. The particle size of the lithium manganate material is 3-16 μm, 5-15 μm, 8-10 μm and 9-10 μm, and specifically, the particle size of the lithium manganate material is 3 μm, 5 μm, 8 μm, 10 μm, 11 μm, 13 μm, 15 μm and 16 μm. The specific surface area of the lithium manganate material is 0.2-15 square meters per gram, 3-13 square meters per gram, 5-10 square meters per gram, 5-8 square meters per gram, 6-8 square meters per gram, and specifically, the specific surface area of the lithium manganate material is 0.2 square meters per gram, 2 square meters per gram, 4 square meters per gram, 5 square meters per gram, 8 square meters per gram, 9 square meters per gram, 10 square meters per gram, 12 square meters per gram, 15 square meters per gram, and 16 square meters per gram.
2. The preparation method of the lithium manganate material can be used for batch production and has good controllability.
A preparation method of a lithium manganate material comprises the following steps:
step S1, lithium salt, manganese salt and doped metal element salt are mixed according to the chemical formula LiA x Mn (2-x) B y O (4-y) Preparing a mixed solution A with the metal ion concentration of 0.5-4 mol/L according to the molar ratio; preparing a precipitating agent and an anion doping agent into a solution B with the concentration of 0.5-6 mol/L according to the ratio of 1: y; preparing a pH regulator into a solution C with the concentration of 1-6 mol/L; preparing a surfactant into a solution D with the concentration of 0.1-10 g/L;
step S2, adding the solution D into a solvent, stirring, adding the mixed solution A and the solution B, stirring and mixing to obtain a treatment solution;
step S3, adding the solution C into the treatment liquid to adjust the pH value, aging, washing, filtering and drying to obtain a lithium manganate precursor;
and step S4, heating, sintering and cooling the lithium manganate precursor to obtain the lithium manganate material.
During preparation, the mixed solution A, the solution B, the solution C and the solution D with certain concentrations are prepared, then mixing and stirring are carried out to react to obtain a reaction product, and the concentration in the reaction liquid can influence the performance of the reaction product in the process, so that the performance of the lithium manganate material can be influenced. The surfactant is used for preparing the solution D, so that the surface tension of a reaction liquid phase system can be reduced, and the dispersion uniformity of the slurry can be improved. The preparation method of the invention carries out anion and cation double doping on the lithium manganate, has simple process and can be produced in large scale.
Preferably, in the step S4, the heating rate is 1-6 ℃/min, the sintering temperature is 400-900 ℃, and the sintering time is 2-20 hours. The heating rate is 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, the sintering temperature is 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃,
preferably, the pH value in the step S3 is 7-11, and the aging time is 5-10 hours. The pH value is 7, 8, 9, 10 and 11, and the aging time is 5 hours, 6 hours, 7 hours, 8 hours, 9 hours and 10 hours.
Preferably, in the step S2, the stirring speed is 800-1200 rpm/min, the stirring time is 40-60 min, and the feeding flow rate of the mixed solution A and the mixed solution B is 10-25 ml/min. Stirring speed is 800rpm/min, 900rpm/min, 1000rpm/min, 1100rpm/min, 1200rpm/min, stirring time is 40min, 45min, 50min, 55min, 60min, and feeding flow rate of the mixed solution A and the mixed solution B is 10ml/min, 15ml/min, 18ml/min, 20ml/min, 25 ml/min.
Preferably, the anion dopant is one or more of ammonium fluoride, ammonium chloride, sodium chloride, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate and sodium phosphate; the precipitant is one or more of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate and ammonium bicarbonate.
3. The secondary battery has good service life and performance.
The secondary battery comprises the lithium manganate material.
The secondary battery has a multi-charge-discharge platform characteristic in a charge-discharge curve during charge-discharge at 3.0-4.2V 0.1C.
Preferably, when the positive plate of the secondary battery is charged and discharged at 3.0-4.2V 0.1C, the charging and discharging platform interval is 4.1V-4.2V, the capacity ratio is 30-38%, the capacity ratio of 4.0V-4.1V is 30-38%, the capacity ratio of 3.85V-4.0V is 26-30%, and the capacity ratio of 3.2V-3.4V is 0-4%.
Preferably, the secondary battery has a charge-discharge plateau region of 4.1V to 4.2V and a capacity occupying ratio of 32 to 35%.
Preferably, the secondary battery has a charge-discharge plateau region of 4.0V to 4.1V and a capacity occupying ratio of 32 to 35%.
Preferably, the secondary battery has a charge-discharge plateau region of 3.85V to 4.0V and a capacity ratio of 27 to 29%.
Preferably, the secondary battery has a charge-discharge plateau region of 3.2V to 3.4V and a capacity ratio of 0 to 2%.
Preferably, the curve of dQ/dV of the secondary battery has a redox peak at a position of 3.2V to 3.6V.
A secondary battery can be a lithium ion battery, a sodium ion battery, a magnesium ion battery, a calcium ion battery, a potassium ion battery. Preferably, the secondary battery is a lithium ion battery, and 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 installing the positive plate, the negative plate, the diaphragm and the electrolyte. The positive plate comprises a positive current collector and a positive active material layer arranged on the surface of the positive current collector, the positive active material layer comprises a positive active material, and the positive active material comprises the lithium manganate material.
Negative electrode
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 (1). 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, control of H in the electrolyte 2 At least one of additives of O and HF content, additives for improving low temperature performance, and multifunctional additives.
The separator may be any material suitable for a lithium ion battery separator in the art, and for example, may be a combination including, but not limited to, one or more of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fiber, and the like.
Preferably, the material of casing is one of stainless steel, plastic-aluminum membrane. More preferably, the housing is an aluminum plastic film.
Because the lithium manganate material has the XRD structure and good structural stability, after the lithium manganate material is prepared into a battery, a charge-discharge curve has a plurality of charge-discharge platforms, particularly the discharge platforms exist at a low potential of 3.2V-3.6V, and meanwhile, in a dQ/dV curve diagram, an obvious reduction oxidation peak exists at a position of 3.2V-3.6V. Due to the electrochemical property of the lithium manganate under the low potential, the oxidation-reduction reaction of transition metal elements under the high potential is inhibited, the structural damage of the material under the high potential is reduced, and particularly the dissolution of Mn elements caused by the structural damage of the material is reduced, so that the battery prepared from the material has good cycle performance.
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
84.8g of LiCl and 542.6g of MnSO are weighed 4 ·H 2 O、159.9gFe 2 (SO 4 ) 3 、135.2gAl 2 (SO 4 ) 3 ·18H 2 Dissolving O in 2000g of deionized water at 50 ℃, and diluting to 3L to obtain a mixed solution A; 487.6g of Na were weighed 2 CO 3 And 46.1gNH 4 H 2 PO 4 Dissolving 2000g of deionized water at the temperature of about 50 ℃, and then fixing the volume to 3L to obtain a solution B; preparing 2L of 6mol/L ammonia water solution, namely weighing 700g of 25% ammonia water solution, and fixing the volume to 2L to obtain solution C; and weighing 6g of high molecular surfactant glycerol according to 0.1 percent of the total volume of the mixed solution A and the solution B, and dissolving the glycerol with 3L of deionized water to obtain a solution D. Adding the solution D into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm/min; simultaneously adding the solution A and the solution B by using a peristaltic pump at a feeding speed of 10ml/min, feeding for 3.5h, adding 5mol/L ammonia water solution by using the peristaltic pump at a feeding speed of 20ml/min after the feeding is finished, adjusting the pH value to a specified value of 8, keeping the stirring speed at 800rpm, aging for 7h, and centrifuging and filtering the slurry by using a centrifuge (model YLT-1200) to obtain a filter cake; placing the filter cake inDrying at 80 deg.C for 3 hr in an electrothermal blowing drier (model 101-0ABS), taking out, placing the precursor of lithium manganate in a muffle furnace (Sigma ML-6000), heating to 800 deg.C within 3 hr, maintaining at air atmosphere for 5 hr, naturally cooling, and pulverizing to obtain LiMn 1.6 Fe 0.2 Al 0.2 [(PO 4 ) 0.2 O 3.8 ]Lithium manganate material, noted as B1.
The following performance tests were performed on the prepared lithium manganate material B1.
(1) Particle size analysis
The particle size of the precursor with a single crystal phase structure prepared in example 1 was measured with a laser particle size measuring instrument (model Mastersizer 3000E); the detection conditions are as follows: water is used as dispersoid, wet sampling is carried out, the refractive index is 2.0, the absorption rate is 0.1, and the obtained particle size is the particle size statistical result of volume integral, which is shown in figure 2.
As can be seen from fig. 2, the particle size distribution of the lithium manganate in example 1 is a normal distribution, in which D50 is 3.64(D10 is 1.42, D50 is 3.64, and D90 is 7.99).
(2) XRD analysis
The crystal phase structure of the lithium manganate material prepared in example 1 was detected by an X-ray diffractometer (model Ultima IV); the detection conditions are as follows: angle range: 10-50 °, scan time: 23min, voltage is: 10kv, the current is 5mA, and the detection result is shown in FIG. 1.
Lithium manganate characteristic peak: characteristic peak a: 18 ° -19 °, characteristic peak B: 22-26 °, characteristic peak C: 26-30 °, characteristic peak D: 30-35 ° and characteristic peak E: 36 ° -37 °, characteristic peak F: 43.5-44.5 degrees; the peak intensity ratio I (B/a) of characteristic peak B to characteristic peak a was 0.03.
(3) Specific surface analysis
The lithium manganate material obtained in example 1 was measured for specific surface area by a specific surface area meter (Jingwei Gaobo JW-BK300) with reference to the following standard: GB/T13390.
The detection conditions are as follows:
adsorbate high purity N2;
sample size of about 3.0-3.5 g (to the nearest 0.0001); the heating temperature is 100 ℃:
the heating time is 1 h.
The results are shown in Table 1.
(4) Analysis of half-cell Electrical Properties
The lithium manganate obtained in example 1 was subjected to half-cell electrical property analysis (4.2-3.0V 0.1C), and the results are shown in FIG. 3. The charge-discharge platform has more than 1 charge-discharge platform, the charge-discharge platform interval is 4.1V-4.2V, the capacity ratio is 30-38%, the capacity ratio of 4.0V-4.1V is 30-38%, the capacity ratio of 3.85V-4.0V is 26-30%, and the capacity ratio of 3.2V-3.4V is 0-4%.
(5) And (3) testing the cycle performance of the battery: the prepared battery was subjected to a cycle performance test, and the test results are shown in fig. 5. As can be seen from FIG. 5, the cycle frequency of the lithium manganate material reaches 600 times under the condition of charging and discharging of 4.2C RT1C and under the condition that the capacity retention rate is not less than 80%, and the cycle performance is improved by 50% compared with 400 times of the comparative example.
Preparing a battery: taking the weight ratio of a positive electrode material B1, acetylene black and PVDF as 100:4:5 dissolving in N-methyl pyrrolidone, stirring, coating on aluminum foil, baking at 100 + -5 deg.C, rolling to a certain thickness with a tablet machine, and rolling to obtain positive plate; graphite, acetylene black and PVDF are mixed in a weight ratio of 100:3:6, dissolving in N-methyl pyrrolidone, uniformly stirring, coating on a copper foil, baking at the temperature of 100 +/-5 ℃, rolling to a certain thickness by using a tablet press, and rolling and cutting into a negative plate; winding the positive and negative electrode plates and a polypropylene diaphragm with the thickness of 16 mu m into a square lithium ion battery core, collecting the lithium ion battery core in a battery case, welding the lithium ion battery core, and then injecting 1.0mol/L LiPF 6 And (EC + EMC + DMC) (wherein the mass ratio of EC, EMC and DMC is 1:1:1) electrolyte, and sealing to obtain the lithium battery B2. The charging limit voltage of the battery is 4.0-5.0V.
Example 2
137.9g of LiNO was weighed 3 339.1g of MnSO 4 ·H 2 O、528.1gNiSO 4 ·6H 2 Dissolving O in 2000g of deionized water at 50 ℃, and diluting to 3L to obtain a mixed solution A; 400.0g of NaOH and 29.6g of NH were weighed out 4 F, dissolving 2000g of deionized water at the temperature of about 50 ℃, and then fixing the volume to 3L to obtain a solution B; preparation of2L of 5mol/L ammonia water solution, namely weighing 350g of 25% ammonia water solution, and fixing the volume to 2L to obtain solution C; and weighing 6g of glycerol according to 0.1 percent of the total volume of the mixed solution A and the solution B, and dissolving the glycerol by using 3L of deionized water to obtain a solution D. Adding the solution D into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm/min; simultaneously adding the mixed solution A and the solution B into a peristaltic pump at a feeding speed of 10ml/min for feeding for 3.5 hours, adding 5mol/L ammonia water solution into the peristaltic pump at a feeding speed of 20ml/min after the feeding is finished, adjusting the pH value to a specified value of 8, keeping the stirring speed at 800rpm/min unchanged, aging the mixture for 7 hours, and centrifugally filtering the slurry by using a centrifugal machine (model YLT-1200) to obtain a filter cake; placing the filter cake in an electrothermal blowing dryer (model 101-0ABS) to dry at a constant temperature of 80 ℃ for 3h, taking out, placing the lithium manganate precursor in a muffle furnace (Sigma ML-6000), heating to 700 ℃ within 3h, preserving heat for 5h under the air atmosphere, naturally cooling, and then performing airflow pulverization to obtain LiMnNi [ (F) Ni [ (F) 2 ) 0.2 O 3.8 ]The lithium manganate material is marked as C1.
Preparing a battery: taking the weight ratio of a positive electrode material C1, acetylene black and PVDF as 100:4:5 dissolving in N-methyl pyrrolidone, stirring, coating on aluminum foil, baking at 100 + -5 deg.C, rolling to a certain thickness with a tablet machine, and rolling to obtain positive plate; dissolving graphite, acetylene black and PVDF in a weight ratio of 100:3:6 in N-methyl pyrrolidone, uniformly stirring, coating on a copper foil, baking at the temperature of 100 +/-5 ℃, rolling to a certain thickness by using a tablet press, and rolling and cutting into a negative plate; winding the positive and negative electrode plates and a polypropylene diaphragm with the thickness of 16 mu m into a square lithium ion battery core, collecting the lithium ion battery core in a battery case, welding the lithium ion battery core, and then injecting 1.0mol/L LiPF 6 And (EC + EMC + DMC) (wherein the mass ratio of EC, EMC and DMC is 1:1:1) electrolyte, sealing and preparing the lithium battery C2.
Example 3
220.1g of Li are weighed out 2 SO 4 661.3g of MnSO 4 ·H 2 O、142.5gCe 2 (SO 4 ) 3 ·8H 2 Dissolving O in 2000g of deionized water at 50 ℃, and then carrying out constant volume treatment to 3L to obtain a mixed solution A; 519.4g of Na were weighed 2 CO 3 And 21.4gNH 4 Dissolving Cl and 2000g of deionized water at 50 ℃, and then fixing the volume to 3L to obtain solution B; 2L of 5mol/L ammonia water solution is prepared, namely 350g of 25% ammonia water solution is weighed, and the volume is fixed to 2L to obtain solution C; and weighing 6g of high molecular surfactant glycerol according to 0.1 percent of the total volume of the mixed solution A and the solution B, and dissolving the glycerol by using 3L of deionized water to obtain a solution D. Adding the solution D into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm/min; simultaneously adding the mixed solution A and the solution B into a peristaltic pump at a feeding speed of 10ml/min for feeding for 3.5 hours, adding 5mol/L ammonia water solution into the peristaltic pump at a feeding speed of 20ml/min after the feeding is finished, adjusting the pH value to a specified value of 8, keeping the stirring speed at 800rpm unchanged, aging the mixture for 4 hours, and centrifuging and filtering the slurry by using a centrifuge (model YLT-1200) to obtain a filter cake; putting the filter cake into an electrothermal blowing dryer (type 101-0ABS) to dry for 3h at the constant temperature of 80 ℃, taking out, putting the lithium manganate precursor into a muffle furnace (Sigma ML-6000), heating to 750 ℃ within 3h, preserving the heat for 6 h under the air atmosphere, naturally cooling, and then performing airflow pulverization to obtain LiMn 1.9 Ce0.1[(Cl 2 ) 0.1 O 3.9 ]Lithium manganate material, noted as D1.
Preparing a battery: dissolving a positive electrode material D1, acetylene black and PVDF in a weight ratio of 100:4:5 in N-methylpyrrolidone, uniformly stirring, coating on an aluminum foil, baking at the temperature of 100 +/-5 ℃, rolling to a certain thickness by using a tablet machine, and rolling to form a positive electrode sheet; dissolving graphite, acetylene black and PVDF in N-methyl pyrrolidone in a weight ratio of 100:3:6, uniformly stirring, coating on a copper foil, baking at the temperature of 100 +/-5 ℃, rolling to a certain thickness by using a tablet press, and rolling and cutting into a negative plate; winding the positive and negative electrode plates and a polypropylene diaphragm with the thickness of 16 mu m into a square lithium ion battery core, collecting the lithium ion battery core in a battery case, welding the lithium ion battery core, and then injecting 1.0mol/LLIPF 6 And (EC + EMC + DMC) (wherein the mass ratio of EC, EMC and DMC is 1:1:1) electrolyte, and sealing to obtain the lithium battery D2.
Example 4
The difference from example 1 is that: in the step S4, the heating rate is 4.4 ℃/min, the sintering temperature is 900 ℃, and the sintering time is 5 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is that: in the step S4, the heating rate is 4.4 ℃/min, the sintering temperature is 600 ℃, and the sintering time is 5 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is that: in the step S4, the heating rate is 4.4 ℃/min, the sintering temperature is 500 ℃, and the sintering time is 8 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that: in the step S4, the heating rate is 4.4 ℃/min, the sintering temperature is 800 ℃, and the sintering time is 3 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that: in the step S3, the pH value is 7, and the aging time is 8 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that: in the step S3, the pH value is 10, and the aging time is 8 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is that: in the step S3, the pH value is 11, and the aging time is 4 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
Comparative example: commercial lithium manganate LiMn 2 O 4 And is marked as A1.
Preparing a battery: dissolving the anode material A1, acetylene black and PVDF in a weight ratio of 100:4:5 in N-methylpyrrolidone, uniformly stirring, coating on an aluminum foil, baking at a temperature of 100 +/-DEGRolling to a certain thickness by using a tablet machine at 5 ℃, and rolling and cutting into a positive plate; dissolving graphite, acetylene black and PVDF in a weight ratio of 100:3:6 in N-methyl pyrrolidone, uniformly stirring, coating on a copper foil, baking at the temperature of 100 +/-5 ℃, rolling to a certain thickness by using a tablet press, and rolling and cutting into a negative plate; winding the positive and negative electrode plates and a polypropylene diaphragm with the thickness of 16 mu m into a square lithium ion battery core, collecting the lithium ion battery core in a battery case, welding the lithium ion battery core, and then injecting 1.0mol/LLIPF 6 And (EC + EMC + DMC) (wherein the mass ratio of EC, EMC and DMC is 1:1:1) electrolyte, and sealing to obtain the lithium battery A2.
And (3) performance testing: the positive electrode active materials and the secondary batteries prepared in examples 1 to 10 and comparative example 1 were subjected to performance tests on particle size distribution, specific surface area, compacted density, and capacity retention rate, and the test results are reported in table 1.
1. Specific surface analysis
The specific surface area of the lithium manganate material prepared above is measured by a specific surface measuring instrument (Jingwei Gaobo JW-BK300), and the reference standard is as follows: GB/T13390.
The detection conditions are as follows:
adsorbate high-purity N2;
sample size of about 3.0-3.5 g (to the nearest 0.0001); the heating temperature is 100 ℃:
the heating time is 1 h.
The results are shown in Table 1.
TABLE 1
As can be seen from table 1 and fig. 5, the lithium manganate material produced according to the present invention has good structural stability and cycle performance, compared to the lithium manganate material of comparative example 1. The secondary battery of the invention is cycled under the condition of RT4.2V-2.85V 1C/1C, after 600 cycles, the capacity retention rate is still more than or equal to 80%, and the capacity retention rate of comparative example 1 is reduced to 80% after 400 cycles. From the comparison of examples 1 to 3, it can be seen that when the lithium manganate material is doped with the metal elements of Fe and Al and anion chloride, the obtained material has better performance.
When a conventional commercially available lithium manganate material is prepared into a button battery and is charged and discharged at 3.0-4.2V 0.1C (see figure 3), only one platform exists in a 3.85-3.0V range, the voltage change is rapid, and Li ions on the interface of the lithium manganate material are easy to generate the problems of over-insertion or over-release, so that the local structure of lithium manganate collapses, and finally the capacity of the lithium manganate battery is attenuated and the cycle performance is poor. As can be seen from fig. 3, the button cell in embodiment 1 of the present invention has multiple plateau characteristics during charging and discharging at 3.0-4.2V 0.1C, which can effectively alleviate the problem of lithium manganate material interface Li ion over-insertion or over-desorption, thereby improving the cycle performance of lithium manganate material. As can be seen from FIG. 4, the lithium manganate material prepared in example 1 of the present invention has a distinct redox peak at the position of 3.2-3.6V.
As shown by comparison of examples 1 and 4-7, when the temperature rise rate is 4.4 ℃/min, the sintering temperature is 800 ℃, and the sintering time is 5 hours in step S4, the prepared material has better performance, the performance and structure stability of the sintered material is better, and the material can still maintain good charge and discharge performance after multiple charge and discharge cycles.
From comparison of examples 1 and 8-10, it is found that when the ph value is 7 and the aging time is 8 hours in step S3, the prepared material has better performance, and the particles obtained in a suitable ph value environment and aging time have more uniform doping distribution and more stable structure, and can still maintain good charge and discharge performance after many charge and discharge cycles.
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. The lithium manganate material is characterized in that the structure of the lithium manganate material is a spinel structure, and an XRD spectrogram of the lithium manganate material has the following characteristic peaks under a 2theta diffraction angle: characteristic peak a: 18 ° -19 °, characteristic peak B: 22-26 °, characteristic peak C: 26-30 °, characteristic peak D: 30-35 °, characteristic peak E: 36 ° -37 °, characteristic peak F: 43.5-44.5 °; the peak intensity ratio I of the characteristic peak B to the characteristic peak A is more than or equal to 0 and less than or equal to 0.5.
2. The lithium manganate material of claim 1, wherein said lithium manganate material is represented by the formula: LiA x Mn (2-x) B y O (4-y) ，0<x<2，0<y<4, A is a metal doping element, and the metal doping element is one or more of Al, Ni, Co, Fe, Ti, Sb, Nb, Y and Ce; b is a non-metal anion, and the non-metal anion is NO 3 - 、Cl - 、F - 、PO 4 3- 、SiO 3 2- One or more than one of them.
3. The lithium manganate material of claim 1, wherein said lithium manganate material has a charge-discharge cutoff voltage of 4.0V to 5.0V.
4. The lithium manganate material of claim 2, wherein the metal doping element accounts for 0.1-20% of the lithium manganate material by weight.
5. The lithium manganate material of claim 1, wherein said lithium manganate material has a median particle diameter D50 of 3 μm to 16 μm, and a specific surface area of 0.2 square meter per gram to 15 square meters per gram.
6. A method for preparing a lithium manganate material as set forth in any of claims 1 to 5, characterized by comprising the steps of:
step S1, lithium salt, manganese salt and doped metal element salt are mixed according to the chemical formula LiA x Mn (2-x) B y O (4-y) Preparing a mixed solution A with the metal ion concentration of 0.5-4 mol/L according to the molar ratio; preparing a precipitating agent and an anion doping agent into a solution B with the concentration of 0.5-6 mol/L according to the ratio of 1: y; preparing a pH regulator into a solution C with the concentration of 1-6 mol/L; preparing a surfactant into a solution D with the concentration of 0.1-10 g/L;
step S2, adding the solution D into a solvent, stirring, adding the mixed solution A and the solution B, stirring and mixing to obtain a treatment solution;
step S3, adding the solution C into the treatment liquid to adjust the pH value, aging, washing, filtering and drying to obtain a lithium manganate precursor;
and step S4, heating, sintering and cooling the lithium manganate precursor to obtain the lithium manganate material.
7. The method for preparing a lithium manganate material of claim 6, wherein in the step S4, the temperature rise rate is 1-6 ℃/min, the sintering temperature is 400-900 ℃, and the sintering time is 2-20 hours.
8. The method for preparing a lithium manganate material according to claim 6, wherein in said step S3, the pH value is 7 to 11, and the aging time is 5 to 10 hours.
9. A secondary battery comprising the lithium manganate material according to any of claims 1 to 5.
10. The secondary battery according to claim 9, wherein the secondary battery has a multi-charge-discharge plateau at a charge-discharge curve of 3.0-4.2V 0.1C, the charge-discharge curve is 4.1V-4.2V, a capacity ratio of 30-38%, a capacity ratio of 4.0V-4.1V of 30-38%, a capacity ratio of 3.85V-4.0V of 26-30%, and a capacity ratio of 3.2V-3.6V of 0-4%.
11. The secondary battery according to claim 9, wherein a redox peak is present at a position of 3.2V to 3.6V in a dQ/dV curve of the secondary battery.
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