CN108767252A - A kind of lithium ion battery - Google Patents
A kind of lithium ion battery Download PDFInfo
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- CN108767252A CN108767252A CN201810167436.8A CN201810167436A CN108767252A CN 108767252 A CN108767252 A CN 108767252A CN 201810167436 A CN201810167436 A CN 201810167436A CN 108767252 A CN108767252 A CN 108767252A
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- lithium ion
- ion battery
- limn2o4
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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Abstract
The present invention relates to high magnification, the lithium ion batteries of high circulation performance, belong to lithium battery design preparing technical field.The lithium ion battery includes positive active material, negative electrode active material；The positive active material is LiMn2O4 and/or the LiMn2O4 doped with M element.The preparation method of the positive active material is：First water-soluble manganese salt+water solubility doped metal salt M is added in lye together, is mixed, is obtained sediment, wash, be dried to obtain standby material；Then match and take lithium source and standby material；Pass through sanded treatment；Mixture after being sanded；Then slurry is made after gained mixture being mixed with liquid；And using gained slurry as raw material；Spherical precursor powder is made using electric jet technology；Finally under the conditions of oxygen-containing, gained spherical precursor powder is heat-treated；It obtains high magnification spherical lithium manganate and is assembled into battery.Present invention process is simple, and products obtained therefrom quality is controllable, function admirable, is convenient for large-scale industrialization application.
Description
Technical field
The present invention relates to high magnification, the lithium ion batteries of high circulation performance, belong to lithium battery design preparing technical field.
Background technology
In the modern life of economic society sustainable development, people to the electronic devices such as mobile phone, notebook and it is electronic from
Driving, electric vehicle demand but gradually increase, non-renewable resources such as oil, natural gas etc. far can not meet people
The demand of class, lithium ion battery is due to the advantages that operating voltage is higher, and cycle life is longer, and self-discharge rate is smaller and in power electric
Pond field has been to be concerned by more and more people, meanwhile, along with extensive use of the lithium ion battery in life, people are for lithium
The requirement of ion battery is also promoted therewith.As typical anode material for lithium-ion batteries, LiMn2O4 is due to resourceful, synthesis
Simply, the advantages that safety and environmental protection and as the hot spot material studied at present, still, LiMn2O4 will appear crystalline substance in charge and discharge process
Body structural stability and invertibity are poor, so as to cause LiMn2O4 cycle performance is poor, capacity attenuation is very fast, this is directly limited
Extensive use and development of the LiMn2O4 in lithium ion battery.In general, LiMn2O4 cycle performance and high rate performance are influenced
The main reason for have：(1) manganese salt easily occurs to dissolve and its structure is caused to change in charge and discharge process.(2) it is preparing
In the process, it is easy to dephasign occur, to influence the stability of phase structure.(3) electrolyte is easily decomposed.(4) material sheet
There are Jahn-Teller effects for body.In order to solve the problems, such as LiMn2O4 appeared in charge and discharge process, the present invention uses metal
Ion doping improves cycle performance and high rate performance of the spinel lithium manganate in repeated charge and discharge process.
Prepared LiMn2O4 is generally random microstructure both at home and abroad at present, prepared lithium manganate particle compared with
Greatly, very serious agglomeration is had if even if preparing grain size smaller LiMn2O4, however also has the manganese of only a few at present
Sour lithium is nano wire, micron ball, and the preparation method of existing spinelle spherical lithium manganate is mainly with manganese carbonate, the oxide of manganese
(manganese dioxide or mangano-manganic oxide), hydroxide nickel cobalt manganese Ni1/3Co1/3Mn1/3(OH)2And cobalt nickel oxide manganses are presoma, so
Afterwards again with lithium source high temperature sintering or as obtained by hydro-thermal reaction preparation.
But it is up to the present, designed and prepare, with LiMn2O4 and/or to adulterate the LiMn2O4 of other elements be positive material
The lithium ion electronics of material either has that preparation process is complicated or has in the presence of cycle and/or high rate performance to be hoisted.
Invention content
The present invention in view of the deficienciess of the prior art, provide a kind of high magnification, high circulation performance lithium ion battery.
A kind of lithium ion battery of the present invention；The lithium ion battery includes positive active material, negative electrode active material；It is described
Positive active material is LiMn2O4 and/or the LiMn2O4 doped with M element；
It the LiMn2O4 and/or is prepared by following proposal doped with the LiMn2O4 of M element：
Step 1
Water-soluble manganese salt is added in lye, is mixed, is obtained sediment, wash, be dried to obtain standby material；
Or
Water-soluble doped metal salt M, water-soluble manganese salt are added in lye, mixed, sediment, washing, drying are obtained
Obtain standby material；
Step 2
With taking standby material obtained by lithium source and step 1；Pass through sanded treatment；Mixture after being sanded；
Step 3
Slurry is made after mixture after being sanded obtained by step 2 is mixed with liquid；
Step 4
Using slurry obtained by step 3 as raw material；Spherical precursor powder is made using electric jet technology；
Step 5
Under the conditions of oxygen-containing, spherical precursor powder obtained by step 4 is heat-treated；Obtain LiMn2O4 and/or doping
There is the LiMn2O4 of M element.
A kind of lithium ion battery of the present invention；The water-soluble manganese salt is in manganese acetate, manganese nitrate, manganese sulfate, manganese chloride
At least one.
A kind of lithium ion battery of the present invention；The water solubility doped metal salt M is selected from nickel nitrate, nickel acetate, nickel chloride, vinegar
At least one of sour cobalt, cobalt nitrate, cobalt chloride.
A kind of lithium ion battery of the present invention；In raw materials used, contain water-soluble doped metal salt M, water-soluble manganese simultaneously
When salt, the molar ratio of water-soluble doped metal salt M and water-soluble manganese salt is 0.01-0.3：1, preferably 0.1:1.
A kind of lithium ion battery of the present invention；In step 1, the lye is sodium hydroxide solution；The sodium hydroxide solution
A concentration of 0.1~4mol/L.
A kind of lithium ion battery of the present invention；In step 1, doped metal salt M and/or manganese salt are added in lye, sky is passed through
It is placed on magnetic stirrer in the case of gas and stirs 3-5h, it, will be obtained after solution fully reacts and generates sediment
Powder carries out centrifuge washing drying；Obtain standby material.
A kind of lithium ion battery of the present invention；In step 2, the molar ratio of lithium source and standby material obtained by step 1 is 1-1.15:
1.For improving performance, dispersant can also be added in step 1, but the addition of dispersant should not be too large；The dispersant choosing
At least one in self-contained sodium carboxymethylcellulose, citric acid, polypropylene phthalein amine, polyvinyl alcohol, polyethylene glycol, polytetrafluoroethylene (PTFE)
Kind.
A kind of lithium ion battery of the present invention；In step 2, when sanded treatment, control rotating speed is that 1200-2500 turns/min；When
Between be 1~10h, the grain size of product is less than 200 nanometers.In the present invention, it is sanded and being uniformly mixed for each material both may be implemented, and
And the grain size and particle diameter distribution that products therefrom is sanded can also be controlled.
A kind of lithium ion battery of the present invention；In step 3,0.5- is incorporated by the mixture after being sanded obtained by every gram of step 2
Mixture after being sanded obtained by step 2 is uniformly mixed with liquid and slurry is made by the ratio of 5ml liquid；The liquid is selected from second
At least one of alcohol, ethylene glycol, propylene glycol.Preferably, the liquid presses volume by ethyl alcohol, ethylene glycol, propylene glycol
Than 1:2:2 compositions.
A kind of lithium ion battery of the present invention；Using slurry obtained by step 3 as raw material；It is loaded into injection apparatus, with 2~
The jet velocity (jet velocity of single-nozzle) of 500mL/h sprays into the raw material in collecting chamber, obtains spherical precursor powder
End；The collecting chamber includes heating plate, injection apparatus reserved opening, nozzle, electric field offer device；The injection apparatus reserved opening is used
It is located at the lower section of nozzle in installation nozzle, the heating plate；The sprayed liquid of nozzle is parallel with direction of an electric field；Collecting chamber works
When, nozzle is anode, collecting board is cathode, and the temperature setting of collecting chamber is between 300-600 DEG C, preferably 300-400 DEG C.?
In R&D process, the setting of other direction electric fields has also been attempted.
A kind of lithium ion battery of the present invention；The distance of heating plate to nozzle is 4~8cm, the voltage of the electric field is 8~
20kV。
A kind of lithium ion battery of the present invention；In air atmosphere, hot place is carried out to spherical precursor powder obtained by step 4
Reason；Obtain high magnification spherical lithium manganate；The temperature of the heat treatment is 500~900 DEG C, and the time is 10~20h.Preferably,
When heat treatment, set temperature is warming up to the heating rate of 1 DEG C/min~10 DEG C/min.
A kind of lithium ion battery of the present invention；Prepared LiMn2O4 and/or it is more than doped with the sphericity of the LiMn2O4 of M element
Equal to 83.6%.LiMn2O4, nickel ion doped, cobalt manganic acid lithium prepared by the present invention and nickle cobalt lithium manganate, by adjusting EFI
Parameter such as flow velocity, the temperature of heating plate and the voltage of high-voltage power supply can be obtained by different-grain diameter and the preferable spherical manganese of dispersibility
Sour lithium material.
Battery that is of the invention designed and preparing, after 500 circle cycles, the capacity retention ratio of battery is 94.7-
95.7%.Far superior to similar product.
Battery that is of the invention designed and preparing, after 800 circle cycles, the capacity retention ratio of battery is 89-92%.
Principle and advantage
The present invention for the first time combines sand milling technology, electric jet technology and subsequent heat treatment to prepare spherical lithium manganate
And/or the spherical lithium manganate of doping, and it is prepared into high-rate lithium battery.In the present invention by selecting suitable EFI to join
Number and suitable heat treatment temperature and soaking time, can obtain the lithium ion cell positive material of different-grain diameter section and soilless sticking
Expect spherical lithium manganate.The preparation process of the method for the present invention is simple, and reaction condition is mild, is easy to prepare on a large scale, as lithium
Ion battery positive electrode, spherical lithium manganate show excellent cyclical stability and high rate performance.Meanwhile the present invention prepares work
Journey controllability strong (as can be accurately adjusted lithium manganate micron ball size by adjusting EFI parameter when industrially applying), peace
Completely without pollution, it is environmental-friendly.
Specific implementation mode
Using the LiMn2O4 prepared by the present invention as active material, by active material, binder (Kynoar PVDF) is led
Electric agent (Super-P) in mass ratio 8:1:1 weighs, and places it in agate mortar be fully ground respectively, it is made to be uniformly mixed
Powder is placed in the bottle of 5mL afterwards, N-Methyl pyrrolidone is added in bottle, is fully divided using high speed dispersor
It places it on magnetic stirrer after stirring 12h and is applied on aluminium foil after dissipating, it is then dry in 60 DEG C of vacuum drying chamber
Pole piece is cut into after 12h.Selected battery case be CR2025, selected cathode be lithium piece, selected electrolyte be containing
LiPF6And volume ratio is 1:1:1 ethyl carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) it is organic
Solvent, selected diaphragm are the polypropylene diaphragms of 16um thickness, and the assembling of battery, selected electricity are finally completed in glove box
It is blue electrical measurement test system that chemical property, which tests system,.
Embodiment one：
First, the NaOH solution for configuring 0.4mol/L, weighs the manganese salt of 2g, is then dissolved into the deionization of 1000mL
In aqueous solution, by alkaline NaOH solution and manganese salt, both solution mix, and are added in reactive tank simultaneously by metering pump,
It is passed through air stirring 3h.Then obtained product deionized water and ethyl alcohol are washed 3 times respectively, finally places the product
The dry 10h in vacuum drying chamber.
Secondly, 1.1 are stoichiometrically weighed:1 weigh respectively lithium salts and it is above-mentioned prepare products therefrom, above-mentioned powder is added
Enter to being sanded in tank, 10h (when sanded treatment, control rotating speed is 1200 turns/min) is sanded, mixed uniformly powder is obtained, by this
Powder is dried.
Again, it is 1 above-mentioned acquired product to be dissolved into volume ratio:2:2 ethyl alcohol, propylene glycol in ethylene glycol, are put
Setting the ultrasound 25min in ultrasonic wave makes it be sufficiently mixed, and the solution mixed is placed in syringe, places a syringe in note
It penetrates on pump, setting flow velocity is 5mL/h, a heating plate is placed below syringe needle, the temperature of heating plate is 300 DEG C, heating plate
The distance between syringe needle is set as 6cm, in addition, also needing the high-voltage power supply of an offer voltage, the voltage of high-voltage power supply is set
It is set to 20kV, 10h is dried in the powder gathered in drying box.
Finally, it is evenly laid out in Noah's ark to weigh the dried powder of certain mass, which is placed in Muffle furnace,
Holding temperature is 700 DEG C, soaking time 10h, and heating rate is 1 DEG C/min, then will be sintered after furnace cooling to room temperature
Powder take out, the sphericity of powder particle is 83.6%.
Method as described above completes the mixing of slurry and the assembling of battery, the cycle performance of battery and forthright again
It can be as shown in Figure 1 and Figure 2 respectively.From figure 1 it appears that after 500 cycles, the capacity retention ratio of battery is more than or equal to
94.7%.
Embodiment two：
First, the NaOH solution for configuring 0.4mol/L, by 1:0.1 stoichiometric ratio weighs manganese salt and nickel salt, then will
It is dissolved into the deionized water solution of 1000mL, and the mixed solution of alkaline NaOH solution and nickel salt, manganese salt is mixed,
Metering pump is added in reactive tank simultaneously, is passed through 3~5h of air stirring.Then by obtained product deionized water and ethyl alcohol
It washs respectively 3 times, the product is finally placed in vacuum drying chamber dry 10h.
Secondly, 1.1 are stoichiometrically weighed:1 weighs lithium salts and product respectively, and above-mentioned powder is added to sand milling tank
In, 10h (when sanded treatment, control rotating speed is 1500 turns/min) is sanded, obtains mixed uniformly powder, which is done
It is dry.
Again, it is 1 above-mentioned acquired product to be dissolved into volume ratio:2:2 ethyl alcohol, propylene glycol in ethylene glycol, are put
Setting the ultrasound 30min in ultrasonic wave makes it be sufficiently mixed, and the solution mixed is placed in syringe, places a syringe in note
It penetrates on pump, sets flow velocity to 2mL/h, a heating plate is placed below syringe needle, the temperature of heating plate is 350 DEG C, heating
Plate is 6cm at a distance from syringe needle, in addition, also needing the high-voltage power supply of an offer voltage, the voltage of high-voltage power supply is set as
10h is dried in the powder gathered by 20kV in drying box.
Finally, it is evenly laid out in Noah's ark to weigh the dried powder of certain mass, which is placed in Muffle furnace,
Holding temperature is 800 DEG C, soaking time 20h, and heating rate is 1 DEG C/min, then will be sintered after furnace cooling to room temperature
Powder take out, the sphericity of powder particle is 83.8%.
Method as described above completes the mixing of slurry and the assembling of battery.After 800 cycles, the capacity of battery
Conservation rate is 91.7%.
Embodiment three：
First, the NaOH solution for configuring 0.4mol/L, by 1:0.1 stoichiometric ratio weighs manganese salt and cobalt salt, then will
It is dissolved into the deionized water solution of 1000mL, by alkaline NaOH solution and cobalt salt, the mixed solution of manganese salt both solution
It mixes, metering pump is added in reactive tank simultaneously, is passed through air stirring 3h.Then by obtained product deionization
Water and ethyl alcohol wash 3 times respectively, and the product is finally placed in vacuum drying chamber dry 10h.
Secondly, 1.1 are stoichiometrically weighed:1 weighs lithium salts and product respectively, and above-mentioned powder is added to sand milling tank
In, 10h (when sanded treatment, control rotating speed is 1800 turns/min) is sanded, obtains mixed uniformly powder, which is done
It is dry.
Again, it is 1 above-mentioned acquired product to be dissolved into volume ratio:2:2 ethyl alcohol, propylene glycol in ethylene glycol, are put
Setting the ultrasound 30min in ultrasonic wave makes it be sufficiently mixed, and the solution mixed is placed in syringe, places a syringe in note
It penetrates on pump, sets flow velocity to 5mL/h, a heating plate is placed below syringe needle, the temperature of heating plate is 350 DEG C, heating
Plate is 6cm at a distance from syringe needle, in addition, also needing the high-voltage power supply of an offer voltage, the voltage of high-voltage power supply is set as
10h is dried in the powder gathered by 20kV in drying box.
Finally, it is evenly laid out in Noah's ark to weigh the dried powder of certain mass, which is placed in Muffle furnace,
Holding temperature is 750 DEG C, soaking time 10h, and heating rate is 1 DEG C/min, then will be sintered after furnace cooling to room temperature
Powder take out.
Method as described above completes the mixing of slurry and the assembling of battery.
Embodiment four：
First, the NaOH solution for configuring 0.4mol/L, by 1：0.1：0.1 stoichiometric ratio weighs manganese salt, nickel salt and cobalt
Then salt is dissolved into the deionized water solution of 1000L, the mixing of alkaline NaOH solution and nickel salt, cobalt salt, manganese salt is molten
Both solution of liquid mix, and metering pump is added in reactive tank simultaneously, is passed through air stirring 3h.It then will be obtained
Product deionized water and ethyl alcohol wash 3~5 times respectively, and the product is finally placed in vacuum drying chamber dry 10h.
Secondly, 1.1 are stoichiometrically weighed:1 weighs lithium salts and product respectively, and above-mentioned powder is added to sand milling tank
In, 10h (when sanded treatment, control rotating speed is 2500 turns/min) is sanded, obtains mixed uniformly powder, which is done
It is dry.
Again, it is 1 above-mentioned acquired product to be dissolved into volume ratio:2:2 ethyl alcohol, propylene glycol in ethylene glycol, are put
Setting the ultrasound 30min in ultrasonic wave makes it be sufficiently mixed, and the solution mixed is placed in syringe, places a syringe in note
It penetrates on pump, sets flow velocity to 5mL/h, a heating plate is placed below syringe needle, the temperature of heating plate is 350 DEG C, heating
Plate is 6cm at a distance from syringe needle, in addition, also needing the high-voltage power supply of an offer voltage, the voltage of high-voltage power supply is set as
10h is dried in the powder gathered by 20kV in drying box.
Finally, it is evenly laid out in Noah's ark to weigh the dried powder of certain mass, which is placed in Muffle furnace,
Holding temperature is 700 DEG C, soaking time 10h, and heating rate is 1 DEG C/min, then will be sintered after furnace cooling to room temperature
Powder take out.
Method as described above completes the mixing of slurry and the assembling of battery.
Comparative example one：
First, the NaOH solution for configuring 0.4mol/L, weighs the manganese salt of 2g, is then dissolved into the deionization of 1000mL
In aqueous solution, by alkaline NaOH solution and manganese salt, both solution mix, and stir 3h.Then obtained product is used
Deionized water and ethyl alcohol wash 3 times respectively, and the product is finally placed in vacuum drying chamber dry 10h.
Secondly, 1.1 are stoichiometrically weighed:1 weigh respectively lithium salts and it is above-mentioned prepare products therefrom, above-mentioned powder is added
Enter to being sanded in tank, 10h (when sanded treatment, control rotating speed is 1200 turns/min) is sanded, mixed uniformly powder is obtained, by this
Powder is dried.
Finally, it is evenly laid out in Noah's ark to weigh the dried powder of certain mass, which is placed in Muffle furnace,
Holding temperature is 700 DEG C, soaking time 10h, and heating rate is 1 DEG C/min, then will be sintered after furnace cooling to room temperature
Powder take out.
Method as described above completes the mixing of slurry and the assembling of battery, cycle performance such as Fig. 3 institutes of battery
Show.Cycle 500 times, capacity retention ratio 47.2%.
Claims (10)
1. a kind of lithium ion battery；It is characterized in that：The lithium ion battery includes positive active material, negative electrode active material；
The positive active material is LiMn2O4 and/or the LiMn2O4 doped with M element；
It the LiMn2O4 and/or is prepared by following proposal doped with the LiMn2O4 of M element：
Step 1
Water-soluble manganese salt is added in lye, is mixed, is obtained sediment, wash, be dried to obtain standby material；
Or
Water-soluble doped metal salt M, water-soluble manganese salt are added in lye, is mixed, is obtained sediment, wash, be dried to obtain
Standby material；
Step 2
With taking standby material obtained by lithium source and step 1；Pass through sanded treatment；Mixture after being sanded；
Step 3
Slurry is made after mixture after being sanded obtained by step 2 is mixed with liquid；
Step 4
Using slurry obtained by step 3 as raw material；Spherical precursor powder is made using electric jet technology；
Step 5
Under the conditions of oxygen-containing, spherical precursor powder obtained by step 4 is heat-treated；Obtain LiMn2O4 and/or doped with M
The LiMn2O4 of element.
2. a kind of lithium ion battery according to claim 1；It is characterized in that：
The water-soluble manganese salt is selected from least one of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride；
The water solubility doped metal salt M in nickel nitrate, nickel acetate, nickel chloride, cobalt acetate, cobalt nitrate, cobalt chloride extremely
Few one kind；
In raw materials used, when containing water-soluble doped metal salt M, water-soluble manganese salt simultaneously, water-soluble doped metal salt M and water
The molar ratio of dissolubility manganese salt is 0.01-0.3：1.
3. a kind of lithium ion battery according to claim 1；It is characterized in that：
In step 1, the lye is sodium hydroxide solution；A concentration of 0.1~4mol/L of the sodium hydroxide solution；
In step 1, doped metal salt M and/or manganese salt are added in lye, magnetic agitation is placed in the case of being passed through air
3-5h is stirred on machine, and after solution fully reacts and generates sediment, obtained powder is subjected to centrifuge washing drying；It obtains
Standby material.
4. a kind of lithium ion battery according to claim 1；It is characterized in that：In step 2, lithium source and step 1 gained
The molar ratio of standby material is 1-1.15:1.
5. a kind of lithium ion battery according to claim 1；It is characterized in that：In step 2, when sanded treatment, control turns
Speed is that 1200-2500 turns/min；Time is 1~10h, and the grain size of product is less than 200 nanometers.In the present invention, being sanded both can be with
It realizes being uniformly mixed for each material, and the grain size and particle diameter distribution that products therefrom is sanded can also be controlled.
6. a kind of lithium ion battery according to claim 1；It is characterized in that：In step 3, obtained by every gram of step 2
The ratio of mixture supplying 0.5-5ml liquid after sand milling, the mixture after being sanded obtained by step 2 is uniformly mixed with liquid
Slurry is made；The liquid is selected from least one of ethyl alcohol, ethylene glycol, propylene glycol.
7. a kind of lithium ion battery according to claim 1；It is characterized in that：Using slurry obtained by step 3 as raw material；It will
It is fitted into injection apparatus, sprays into collecting chamber the raw material with the jet velocity of 2~500mL/h, obtains spherical precursor
Powder；The collecting chamber includes heating plate, injection apparatus reserved opening, nozzle, electric field offer device；The injection apparatus reserved opening
For installing nozzle, the heating plate is located at the lower section of nozzle, and the distance of heating plate to nozzle is 4~8cm；Nozzle is sprayed
Liquid is parallel with direction of an electric field；When collecting chamber works, nozzle is anode, collecting board is cathode, and the temperature setting of collecting chamber exists
Between 300-600 DEG C；The voltage of the electric field is 8~20kV.
8. a kind of lithium ion battery according to claim 1；It is characterized in that：In air atmosphere, to obtained by step 4
Spherical precursor powder is heat-treated；Obtain high magnification spherical lithium manganate；The temperature of the heat treatment is 500~900 DEG C, when
Between be 10~20h.Preferably, when heat treatment, set temperature is warming up to the heating rate of 1 DEG C/min~10 DEG C/min.
9. a kind of lithium ion battery according to claim 1；It is characterized in that：Prepared LiMn2O4 and/or doped with M member
The sphericity of the LiMn2O4 of element is more than or equal to 95%.
10. a kind of lithium ion battery according to claim 1；It is characterized in that：
For the lithium ion battery after 500 circle cycles, the capacity retention ratio of battery is 94.7-95.7%；
The lithium ion battery is through after 800 circle cycles, the capacity retention ratio of battery is 89-92%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575187A (en) * | 2018-11-26 | 2019-04-05 | 中南大学 | Crosslinked polymer electrolyte preparation method, semisolid polymer battery and preparation method |
| CN113782746A (en) * | 2021-08-31 | 2021-12-10 | 深圳市泽塔电源系统有限公司 | Preparation process of lithium manganate composite material with ternary shell layer |
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