CN112694132A - ZnMn2O4Negative electrode material, preparation method and application thereof - Google Patents
ZnMn2O4Negative electrode material, preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 43
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 14
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- 239000011701 zinc Substances 0.000 claims abstract description 12
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- 238000001035 drying Methods 0.000 claims description 33
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides ZnMn2O4The negative electrode material, the preparation method and the application thereof are disclosed, wherein the preparation method comprises the following steps: the ZnMn is prepared by using a soft template method by taking a mixed salt solution of a zinc source and a manganese source as a raw material and sucrose as a soft template agent2O4And (3) a negative electrode material. The invention uses sucrose as soft template agent to be added into the raw material and then directly roasted, the preparation process is simple and convenient, the raw material cost is low, and the method is pollution-free, and is feasible ZnMn2O4A preparation method of the electrode material.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials, and relates to ZnMn2O4A negative electrode material, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, no memory effect, long cycle life, environmental friendliness and the like, and is widely applied to the field of portable electronic equipment. In recent years, lithium ion batteries have attracted more and more attention in the field of high-power long-life batteries such as electric vehicles and hybrid electric vehicles. At present, graphite-based negative electrode materials are widely used for lithium ion batteries. On one hand, the carbon-based negative electrode material has the advantages of low price, electrochemical inertia and low charge and discharge platform; on the other hand, the lithium ion intercalation and deintercalation process provides deposition sites and reduces the formation of lithium dendrites. Welna et al use vertically aligned multi-walled carbon nanotubes as active electrode materials to achieve excellent electrochemical performance of lithium ion batteries. However, the theoretical specific capacity of the graphite negative electrode material is only 372mAh/g, the graphite negative electrode material is poor in compatibility with an electrolyte, and the graphite negative electrode material is easy to pulverize and fall off in the charging and discharging process, so that the energy density of the lithium ion battery is not high, and the requirements of a new generation of high-performance lithium ion battery are difficult to meet.
Transition metal oxides have been widely recognized as promising negative electrode materials for lithium ion batteries due to their high theoretical specific capacity, low cost, and environmental friendliness. Zinc manganate (ZnMn)2O4) The electrode material has the excellent characteristics of high specific capacity, abundant natural resources, environmental friendliness, lower working voltage and the like, and is considered to be a lithium ion battery cathode material with great research value and application prospect. In addition, Zn and Mn are different in electrode potential from each other, so that the material can be used as a mutually buffered body in the charge-discharge cycle process, the volume effect is favorably relieved, and the cycle performance of the material is improved.
Preparation of ZnMn at present2O4The electrode material can be prepared by microemulsion method, electrostatic spinning method, hydrothermal method, solvent thermal method, etc.
CN107720829A discloses a preparation method of a lithium ion battery cathode material zinc manganate, wherein oxalic acid is used as a precipitator, and a coprecipitation method is used for preparing the zinc manganate. Specifically, the aqueous solution of manganese salt and zinc salt is slowly dropped into the ethanol solution of oxalic acid, a precursor is obtained through centrifugation, water washing, alcohol washing and vacuum drying, and the zinc manganate is obtained through high-temperature calcination of the precursor.
CN104577110A provides a preparation method of zinc manganate nanofiber negative electrode material for lithium ion battery, the method firstly utilizes electrostatic spinning technology to prepare PAN/PVP/C4H6ZnO4/C4H6MnO4And compounding the nano-fibers, and then calcining at high temperature to obtain the lithium battery cathode material zinc manganate nano-fibers.
CN108400324A discloses a lithium ion battery cathode material zinc manganate nanorod and a preparation method thereof, wherein the method comprises the following steps: calcining MnOOH powder in a tube furnace for 90-120 minutes to obtain beta-MnO2A nanorod; dissolving 2-methylimidazole in a methanol solution to obtain a 2-methylimidazole methanol solution, dissolving zinc nitrate hexahydrate in the methanol solution to obtain a zinc nitrate hexahydrate methanol solution, slowly adding the 2-methylimidazole methanol solution to the zinc nitrate hexahydrate methanol solution to obtain a mixed solution, and then adding the prepared beta-MnO2Dispersing the nano-rods into the mixed solution, and magnetically stirring for 30 minutes to form a suspension; transferring the obtained suspension into a reaction kettle for hydrothermal reaction for 12-15 hours, and carrying out suction filtration, cleaning and drying on a precipitate obtained after the hydrothermal reaction to obtain beta-MnO2A ZIF-8 complex; the obtained beta-MnO2And calcining the/ZIF-8 compound for 2-3 hours to obtain the zinc manganate nanorod.
However, these methods have limited ZnMn due to high cost and complicated preparation process2O4Development and application of negative electrode materials. In conclusion, ZnMn with simple process, high yield, low cost and excellent lithium storage performance is sought2O4The preparation method of the lithium ion battery cathode material is particularly important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide ZnMn2O4The invention relates to a negative electrode material, a preparation method and application thereof, wherein sucrose is used as a soft template agentThe raw materials are directly roasted after being added, the preparation process is simple and convenient, the raw material cost is low, no pollution is caused, and the ZnMn composite material is feasible2O4A preparation method of the electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a ZnMn alloy2O4The preparation method of the negative electrode material comprises the following steps: the ZnMn is prepared by using a soft template method by taking a mixed salt solution of a zinc source and a manganese source as a raw material and sucrose as a soft template agent2O4And (3) a negative electrode material.
The invention uses sucrose as soft template agent to be added into the raw material and then directly roasted, the preparation process is simple and convenient, the raw material cost is low, and the method is pollution-free, and is feasible ZnMn2O4In the preparation method of the electrode material, sucrose initially generates caramelization reaction in the roasting process; when the caramel is continuously heated, a large amount of CO is released by the decomposition of the caramel2And H2O causes the volume to expand rapidly, so the method can be used for preparing ZnMn2O4The soft template agent, the ZnMn prepared2O4The electrode material has the excellent characteristics of high specific capacity, abundant natural resources, environmental friendliness, lower working voltage and the like, and is considered to be a lithium ion battery cathode material with great research value and application prospect. In addition, Zn and Mn are different in electrode potential from each other, so that the material can be used as a mutually buffered body in the charge-discharge cycle process, the volume effect is favorably relieved, and the cycle performance of the material is improved.
As a preferred technical scheme of the present invention, the preparation method specifically comprises:
dissolving a zinc source and a manganese source in deionized water to prepare a mixed salt solution, and mixing and dissolving sucrose and the mixed salt solution to obtain a mixed solution;
(II) transferring the mixed solution to a porcelain boat, drying until a film is formed on the surface of the mixed solution, and then annealing to obtain the ZnMn zinc oxide2O4And (3) a negative electrode material.
In a preferred technical scheme of the invention, in the step (I), the zinc source comprises any one or a combination of at least two of zinc sulfate, zinc chloride or zinc nitrate;
preferably, the manganese source comprises any one of manganese sulfate, manganese chloride or manganese nitrate or a combination of at least two of the same.
As a preferred technical scheme of the invention, in the step (I), the zinc source and the manganese source are ZnMn2O4The stoichiometric ratio is weighed and dissolved in deionized water respectively.
In a preferred embodiment of the present invention, the mass of sucrose is 25 to 35 wt% of the mass of the mixed salt solution, and may be, for example, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, or 35 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
In the invention, the addition amount of sucrose is crucial, the invention particularly limits the mass of sucrose to be 25-35 wt% of the mass of the mixed salt solution, and when the mass of sucrose is lower than the addition amount, a film cannot be formed in the drying process of the raw materials, so that the morphology of the materials is influenced; when the sucrose quality is higher than the addition amount, the solution is not dissolved uniformly, and the morphology and the electrochemical performance of the material are influenced.
In a preferred embodiment of the present invention, in the step (ii), the drying process is performed in a forced air drying apparatus.
Preferably, the drying temperature is 60 to 80 ℃, for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ or 70 ℃, but not limited to the values listed, and other values not listed in the range of the values are also applicable, and more preferably 70 ℃.
Preferably, the drying time is 2 to 3 hours, for example, 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but is not limited to the listed values, and other values within the range are also applicable, and further 2 to 2.5 hours are more preferable.
In a preferred embodiment of the present invention, in the step (ii), the annealing treatment is performed in a muffle furnace;
preferably, the annealing temperature is 500 to 700 ℃, for example, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃ or 700 ℃, but is not limited to the recited values, and other values not recited within the range of values are also applicable, and more preferably 600 ℃.
In the invention, the selection of the annealing temperature is crucial, the annealing temperature is particularly limited to be 500-700 ℃, and when the annealing temperature is lower than 500 ℃, the zinc manganate material can not be generated after annealing and still serves as a manganese source raw material; when the annealing temperature is higher than 700 ℃, the crystal structure of the material is damaged, the morphology of the material is influenced, and the electrochemical performance is further deteriorated.
Preferably, the annealing time is 1 to 3 hours, and may be, for example, 1.0 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable, and further preferably 2 hours.
In the invention, the selection of the annealing time is crucial, the annealing time is particularly limited to 1-3 h, and when the annealing time is less than 1h, a zinc manganate material cannot be generated; when the annealing time is more than 3h, the material is affected on the morphology and the crystal structure of the material under high-temperature conditions for a long time.
In a second aspect, the invention provides a ZnMn2O4Negative electrode material, the ZnMn2O4The negative electrode material is prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides a lithium ion battery, where the lithium ion battery includes a housing and a battery cell located inside the housing, and the battery cell is obtained by sequentially stacking a positive electrode plate, a diaphragm, and a negative electrode plate and then winding or stacking the positive electrode plate, the diaphragm, and the negative electrode plate.
The negative pole piece comprisesNegative electrode current collector and negative electrode slurry coated thereon, wherein the negative electrode slurry comprises ZnMn of the second aspect2O4And (3) a negative electrode material.
As a preferable technical solution of the present invention, the negative electrode slurry further includes a conductive agent and a binder.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses sucrose as soft template agent to be added into the raw material and then directly roasted, the preparation process is simple and convenient, the raw material cost is low, and the method is pollution-free, and is feasible ZnMn2O4In the preparation method of the electrode material, sucrose initially generates caramelization reaction in the roasting process; when the caramel is continuously heated, a large amount of CO is released by the decomposition of the caramel2And H2O causes the volume to expand rapidly, so the method can be used for preparing ZnMn2O4The soft template agent, the ZnMn prepared2O4The electrode material has the excellent characteristics of high specific capacity, abundant natural resources, environmental friendliness, lower working voltage and the like, and is considered to be a lithium ion battery cathode material with great research value and application prospect. In addition, Zn and Mn are different in electrode potential from each other, so that the material can be used as a mutually buffered body in the charge-discharge cycle process, the volume effect is favorably relieved, and the cycle performance of the material is improved.
Drawings
FIG. 1 shows ZnMn prepared in example 3 of the present invention2O4XRD pattern of the negative electrode material.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
This example provides a ZnMn alloy2O4The preparation method of the negative electrode material comprises the following steps:
(1) zinc sulfate and manganese sulfate according to ZnMn2O4Respectively weighing the stoichiometric ratio, dissolving the stoichiometric ratio in 5mL of deionized water to prepare a mixed salt solution, and mixing and dissolving the sucrose and the mixed salt solutionObtaining mixed liquor, wherein the mass of the sucrose is 25 wt% of the mass of the mixed salt solution;
(2) transferring the mixed solution to a porcelain boat, putting the porcelain boat into a forced air drying device for drying treatment, wherein the drying temperature is 60 ℃, the drying time is 3h, after a film is formed on the surface of the mixed solution, transferring the porcelain boat into a muffle furnace for annealing treatment, the annealing temperature is 500 ℃, the annealing time is 3h, and obtaining ZnMn after annealing2O4And (3) a negative electrode material.
Example 2
This example provides a ZnMn alloy2O4The preparation method of the negative electrode material comprises the following steps:
(1) zinc chloride and manganese chloride in accordance with ZnMn2O4Respectively weighing the stoichiometric ratio, dissolving the stoichiometric ratio in 5mL of deionized water to prepare a mixed salt solution, and mixing and dissolving sucrose and the mixed salt solution to obtain a mixed solution, wherein the mass of the sucrose is 27 wt% of the mass of the mixed salt solution;
(2) transferring the mixed solution to a porcelain boat, putting the porcelain boat into a forced air drying device for drying treatment, wherein the drying temperature is 64 ℃, the drying time is 2.8h, transferring the porcelain boat to a muffle furnace for annealing treatment after a film is formed on the surface of the mixed solution, the annealing temperature is 540 ℃, the annealing time is 2.6h, and obtaining ZnMn after annealing2O4And (3) a negative electrode material.
Example 3
This example provides a ZnMn alloy2O4The preparation method of the negative electrode material comprises the following steps:
(1) zinc nitrate and manganese nitrate in accordance with ZnMn2O4Respectively weighing the stoichiometric ratio, dissolving the stoichiometric ratio in 5mL of deionized water to prepare a mixed salt solution, and mixing and dissolving sucrose and the mixed salt solution to obtain a mixed solution, wherein the mass of the sucrose is 29 wt% of the mass of the mixed salt solution;
(2) transferring the mixed solution to a porcelain boat, putting the porcelain boat into a blast drying device for drying treatment at the drying temperature of 68 ℃ for 2.6h, transferring the porcelain boat into a muffle furnace for annealing treatment after a film is formed on the surface of the mixed solution,the annealing temperature is 580 ℃, the annealing time is 2.2h, and ZnMn is obtained after annealing2O4And (3) a negative electrode material.
Preparation of the obtained ZnMn2O4The XRD pattern of the cathode material is shown in figure 1, and as can be seen from figure 1, the diffraction peaks of the sample prepared by the method of direct liquid phase drying and sintering by adopting sucrose as a soft template agent correspond to the diffraction peaks of JCPDS 24-1133 of standard zinc manganate card one by one, which indicates that the prepared sample is ZnMn2O4A material.
Example 4
This example provides a ZnMn alloy2O4The preparation method of the negative electrode material comprises the following steps:
(1) zinc sulfate and manganese chloride according to ZnMn2O4Respectively weighing the stoichiometric ratio, dissolving the stoichiometric ratio in 5mL of deionized water to prepare a mixed salt solution, and mixing and dissolving sucrose and the mixed salt solution to obtain a mixed solution, wherein the mass of the sucrose is 31 wt% of that of the mixed salt solution;
(2) transferring the mixed solution to a porcelain boat, putting the porcelain boat into a forced air drying device for drying treatment, wherein the drying temperature is 72 ℃, the drying time is 2.4h, transferring the porcelain boat to a muffle furnace for annealing treatment after a film is formed on the surface of the mixed solution, the annealing temperature is 620 ℃, the annealing time is 1.8h, and obtaining ZnMn after annealing2O4And (3) a negative electrode material.
Example 5
This example provides a ZnMn alloy2O4The preparation method of the negative electrode material comprises the following steps:
(1) zinc chloride and manganese nitrate in accordance with ZnMn2O4Respectively weighing the stoichiometric ratio, dissolving the stoichiometric ratio in 5mL of deionized water to prepare a mixed salt solution, and mixing and dissolving sucrose and the mixed salt solution to obtain a mixed solution, wherein the mass of the sucrose is 33 wt% of that of the mixed salt solution;
(2) transferring the mixed solution to a porcelain boat, putting the porcelain boat into a blast drying device for drying treatment, wherein the drying temperature is 76 ℃, the drying time is 2.2h, and after a film is formed on the surface of the mixed solution, the porcelain is put into a furnaceThe boat is transferred into a muffle furnace for annealing treatment, the annealing temperature is 660 ℃, the annealing time is 1.4h, and ZnMn is obtained after annealing2O4And (3) a negative electrode material.
Example 6
This example provides a ZnMn alloy2O4The preparation method of the negative electrode material comprises the following steps:
(1) zinc nitrate and manganese sulphate in the form of ZnMn2O4Respectively weighing the stoichiometric ratio, dissolving the stoichiometric ratio in 5mL of deionized water to prepare a mixed salt solution, and mixing and dissolving sucrose and the mixed salt solution to obtain a mixed solution, wherein the mass of the sucrose is 35 wt% of that of the mixed salt solution;
(2) transferring the mixed solution to a porcelain boat, putting the porcelain boat into a forced air drying device for drying treatment, wherein the drying temperature is 80 ℃, the drying time is 2h, after a film is formed on the surface of the mixed solution, transferring the porcelain boat into a muffle furnace for annealing treatment, the annealing temperature is 700 ℃, the annealing time is 1h, and obtaining ZnMn after annealing2O4And (3) a negative electrode material.
Example 7
The difference between this example and example 3 is that in step (1), the mass of sucrose is 20 wt% of the mass of the mixed salt solution, and other process parameters and operation steps are exactly the same as those in example 1.
Example 8
The difference between this example and example 3 is that in step (1), the mass of sucrose is 40 wt% of the mass of the mixed salt solution, and other process parameters and operation steps are exactly the same as those in example 1.
Example 9
The difference between this example and example 3 is that in step (2), the annealing temperature is 450 ℃, and other process parameters and operation steps are exactly the same as those in example 1.
Example 10
The difference between this example and example 3 is that in step (2), the annealing temperature is 750 ℃, and other process parameters and operation steps are exactly the same as those in example 1.
Example 11
The difference between this example and example 3 is that in step (2), the annealing time is 0.5h, and other process parameters and operation steps are exactly the same as those in example 1.
Example 12
The difference between this example and example 3 is that in step (2), the annealing time is 3.5h, and other process parameters and operation steps are exactly the same as those in example 1.
Comparative example 1
The comparative example is a preparation method of a lithium ion battery cathode material zinc manganate disclosed in CN107720829A, and specifically comprises the following steps:
(1) solution preparation: when preparing the solution, 0.01mol of zinc acetate and 0.02mol of manganese sulfate are weighed and dissolved in 100mL of deionized water, 0.15mol of oxalic acid is weighed and dissolved in 100mL of absolute ethyl alcohol, and the mixture is stirred until the solution is completely dissolved.
(2) Solution mixing: slowly dropwise adding an aqueous solution of zinc acetate and manganese sulfate into an ethanol solution of oxalic acid at a dropping speed of 5mL/min under the condition of vigorous magnetic stirring, centrifuging, washing with water and alcohol, and vacuum-drying the precipitate to obtain a precursor;
(3) and (3) high-temperature sintering: calcining the precursor at 600 ℃ for 3h to obtain ZnMn2O4And (3) a negative electrode material.
ZnMn prepared in examples 1 to 12 was used2O4The lithium ion battery is prepared from the negative electrode material by the following method, and the prepared lithium ion battery is tested. The 0.1C discharge gram capacity mAh/g and the circulating capacity retention rate% are tested.
The lithium ion battery is prepared by the following method:
(1) preparing a positive pole piece: the method comprises the steps of fully and uniformly stirring a nickel cobalt lithium manganate positive electrode material, a conductive agent carbon nano tube and a binder polyvinylidene fluoride (PVDF) in an N-methyl pyrrolidone solvent according to a mass ratio of 96:2:2, coating the mixture on an aluminum foil, and drying and cold pressing the aluminum foil to obtain a positive electrode piece.
(2) Preparing a negative pole piece: ZnMn obtained by comparing examples 1-12 and comparative example 12O4The negative pole piece is prepared by the steps of fully stirring and uniformly mixing a negative pole material, a conductive agent acetylene black, a binder Styrene Butadiene Rubber (SBR) and a thickening agent sodium carboxymethyl cellulose (CMC) in deionized water according to a mass ratio of 96:2:1:1, coating the mixture on a copper foil, and drying and cold pressing the mixture.
(3) And (3) isolation film: polyethylene (PE) porous polymeric films were used as separators.
(4) Preparing an electrolyte: 1.2mol/L LiPF6Adding the mixture into a solvent of dimethyl carbonate, diethyl carbonate and ethylene carbonate in a mass ratio of 1:1: 1. And simultaneously adding 2.1 wt% of 1, 3, 6-hexanetrinitrile, succinonitrile and adiponitrile in a mass ratio of 1:1:1 as a high-voltage protection additive.
And stacking the positive pole piece, the isolating film and the negative pole piece in sequence, wherein the diaphragm is positioned between the positive pole and the negative pole to play a role in isolating, and winding or laminating. And (4) placing the battery core in an outer package, injecting electrolyte and packaging.
The prepared lithium ion battery is subjected to the following performance tests:
(1) and (3) capacity testing: ZnMn obtained in 10 each of examples and comparative examples2O4The negative electrode material is made into a lithium ion battery, and the lithium ion battery is charged to 4.4V at room temperature by constant current of 0.1C multiplying power, and then is charged to the current of less than 0.02C under the condition of 4.4V constant voltage, so that the lithium ion battery is in a 4.4V full charge state. Then constant current discharge is carried out to 2.5V under the multiplying power of 0.1C, the discharge capacity is obtained, and the discharge gram capacity is calculated by adopting the following formula:
discharge capacity-discharge capacity/ZnMn2O4Mass of the negative electrode material.
(2) Cycle capacity retention rate test: ZnMn obtained in 10 each of examples and comparative examples2O4The negative electrode material is made into a lithium ion battery, and the lithium ion battery is subjected to charge-discharge cycle through the following test steps:
charging and discharging at room temperature, and performing constant-current and constant-voltage charging at a charging current of 0.5C until the upper limit voltage is 4.4V and the cutoff current is 0.02C; then standing for 20 minutes; then, constant current discharge was performed at a discharge current of 0.5C until 2.5V.
The discharge capacity retention rate of the lithium ion battery is calculated by adopting the following formula:
the cycle capacity retention rate test ═ (discharge capacity at the n-th cycle/discharge capacity at the first cycle) × 100%.
The results of 0.1C gram capacity, first charge and discharge efficiency, and capacity retention after 100 cycles are shown in table 1.
TABLE 1
As can be seen from the data in table 1:
(1) the test results of examples 1-6 and comparative example 1 show that the gram discharge capacity, the first charge-discharge efficiency and the capacity retention rate of the lithium ion batteries obtained in examples 1-6 are all kept at higher levels, even slightly better than that of comparative example 1. The invention uses sucrose as soft template agent to be added into raw material and then directly roasted, and during the roasting process, the sucrose can generate caramelization reaction at first; when the caramel is continuously heated, a large amount of CO is released by the decomposition of the caramel2And H2O causes the volume to expand rapidly, so that the method can be used for preparing ZnMn2O4The soft template agent.
(2) The test results of the embodiment 3, the embodiment 7 and the embodiment 8 show that the gram-discharge capacity, the first charge-discharge efficiency and the capacity retention rate of the lithium ion battery obtained in the embodiment 3 are higher than those of the embodiment 7 and the embodiment 8, because the quality of the sucrose added in the embodiment 7 is too low, and the quality of the sucrose added in the embodiment 8 is too high, the test results show that the too high or too low quality of the sucrose can affect various performances of the lithium ion battery, because when the adding amount of the sucrose is too low, a film cannot be formed in the drying process of the raw material, and the morphology of the material is affected; when the addition amount of sucrose is too high, the solution is not dissolved uniformly, and the morphology and the electrochemical performance of the material are affected.
(3) As is apparent from the test results of examples 3, 9, and 10, the gram discharge capacity, the first charge-discharge efficiency, and the capacity retention rate of the lithium ion battery obtained in example 3 are all higher than those of examples 9 and 10, because the annealing temperature in example 9 is too low, and the annealing temperature in example 10 is too high, the test results show that the annealing temperature is too low or too high, which affects the performances of the lithium ion battery, because when the annealing temperature is too low, the zinc manganate material is not generated after annealing, but remains as a manganese source raw material; when the annealing temperature is too high, the crystal structure of the material is damaged, the morphology of the material is influenced, and the electrochemical performance is further deteriorated.
(3) As is apparent from the test results of the examples 3, 11 and 12, the gram discharge capacity, the first charge-discharge efficiency and the capacity retention rate of the lithium ion battery obtained in the example 3 are all higher than those of the examples 11 and 12, because the annealing time in the example 11 is too short, and the annealing time in the example 12 is too long, the test results show that the annealing time is too long or too short, which affects the performances of the lithium ion battery, because the zinc manganate material cannot be generated when the annealing time is too short; when the annealing time is too long, the material is subjected to high temperature for a long time, and the shape and the crystal structure of the material are influenced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. ZnMn2O4The preparation method of the negative electrode material is characterized by comprising the following steps: taking mixed salt solution of a zinc source and a manganese source as a raw materialThe material is prepared by using cane sugar as a soft template agent and adopting a soft template method to prepare ZnMn2O4And (3) a negative electrode material.
2. The preparation method according to claim 1, wherein the preparation method specifically comprises:
dissolving a zinc source and a manganese source in deionized water to prepare a mixed salt solution, and mixing and dissolving sucrose and the mixed salt solution to obtain a mixed solution;
(II) transferring the mixed solution to a porcelain boat, drying until a film is formed on the surface of the mixed solution, and then annealing to obtain the ZnMn zinc oxide2O4And (3) a negative electrode material.
3. The method according to claim 2, wherein in step (i), the zinc source comprises any one or a combination of at least two of zinc sulfate, zinc chloride or zinc nitrate;
preferably, the manganese source comprises any one of manganese sulfate, manganese chloride or manganese nitrate or a combination of at least two of the same.
4. The process according to claim 2 or 3, wherein in step (I), the zinc source and the manganese source are ZnMn2O4The stoichiometric ratio is weighed and dissolved in deionized water respectively.
5. The method according to any one of claims 1 to 4, wherein the mass of sucrose is 25 to 35 wt% of the mass of the mixed salt solution.
6. The production process according to any one of claims 2 to 5, wherein in the step (II), the drying treatment is carried out in a forced air drying apparatus;
preferably, the drying temperature is 60-80 ℃, and further preferably 70 ℃;
preferably, the drying time is 2-3 h, and further preferably 2-2.5 h.
7. The process according to any one of claims 2 to 6, wherein in the step (II), the annealing treatment is carried out in a muffle furnace;
preferably, the annealing temperature is 500-700 ℃, and more preferably 600 ℃;
preferably, the annealing time is 1-3 h, and more preferably 2 h.
8. ZnMn2O4The negative electrode material is characterized in that ZnMn is adopted2O4The negative electrode material is prepared by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery is characterized by comprising a shell and a battery cell positioned in the shell, wherein the battery cell is obtained by sequentially laminating a positive pole piece, a diaphragm and a negative pole piece and then winding or laminating;
the negative pole piece comprises a negative pole current collector and a negative pole slurry coated on the negative pole current collector, wherein the negative pole slurry comprises ZnMn of claim 82O4And (3) a negative electrode material.
10. The lithium ion battery of claim 9, wherein the negative electrode slurry further comprises a conductive agent and a binder.
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