CN109768268A - Manganate cathode material for lithium and preparation method thereof - Google Patents
Manganate cathode material for lithium and preparation method thereof Download PDFInfo
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- CN109768268A CN109768268A CN201910200277.1A CN201910200277A CN109768268A CN 109768268 A CN109768268 A CN 109768268A CN 201910200277 A CN201910200277 A CN 201910200277A CN 109768268 A CN109768268 A CN 109768268A
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Abstract
The present invention discloses a kind of manganate cathode material for lithium and preparation method thereof, and the preparation method is the following steps are included: take fluoride to do pulverization process；Fluoride and lithium carbonate, manganese source material and boric acid after pulverization process is mixed to get mixture, the mixture is subjected to the once sintered LiMn2O4 for generating fluorine doped；It weighs the LiMn2O4 and aluminium hydroxide of the fluorine doped in proportion, carries out double sintering, generate the manganate cathode material for lithium, the molar ratio of the LiMn2O4 of the fluorine doped and the aluminium hydroxide is 1:0.02 ~ 0.1.The low preparation of preparation method preparation cost provided by the invention is convenient, and the carbonic acid lithium anode material good cycle of preparation, capacity are high.
Description
Technical field
The present invention relates to food-making technology fields, and in particular to a kind of manganate cathode material for lithium and preparation method thereof.
Background technique
The production cost of lithium battery occupies the increasing ratio of electric car production cost.In three big dynamic lithium battery systems
In, the production prices advantage of LiMn2O4 is extremely obvious.LiMn2O4 have it is resourceful, simple production process, production cost is low, nothing
The advantages that pollution, has a safety feature, good rate capability, is the positive electrode that there is developing market prospect in pole.Existing mangaic acid lithium doping
Coating modification means have liquid phase process and solid phase method, use the former mostly at present, but liquid phase method operating process is cumbersome, it is difficult to
Realize industrialized production.And the LiMn2O4 modified effect that solid phase method is modified is poor, specific discharge capacity is low, leads to the energy of lithium manganate battery
Metric density raising not apparent always.
It is therefore desirable to provide a kind of novel manganate cathode material for lithium, to solve the above technical problems.
Summary of the invention
The main object of the present invention is to provide the preparation method and manganate cathode material for lithium of a kind of manganate cathode material for lithium, with
The technical problem that manganate cathode material for lithium modified effect is poor, specific discharge capacity is low is solved made of existing solid phase method.
To achieve the above object, the preparation method of manganate cathode material for lithium proposed by the present invention, comprising the following steps:
Fluoride is taken to do pulverization process；
Fluoride and lithium carbonate, manganese source material and boric acid after pulverization process is mixed to get mixture, by the mixture
Carry out the once sintered LiMn2O4 for generating fluorine doped；
The LiMn2O4 and aluminium hydroxide of the fluorine doped are weighed in proportion, are carried out double sintering, are generated the manganate cathode material for lithium,
The molar ratio of the LiMn2O4 of the fluorine doped and the aluminium hydroxide is 1:0.02 ~ 0.1.
Preferably, the fluoride includes MgF2、AlF3、SiF4It is any one or more of.
Preferably, the median of the fluoride after the pulverization process is 1 ~ 2um.
Preferably, the manganese source material includes any one of manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide or more
Kind.
Preferably, the molar ratio of the Li:Mn:F:B in the mixture is 1:2:(0.02~0.1): 0.01.
Preferably, the fluoride and lithium carbonate by after pulverization process, manganese source material and boric acid are mixed to get mixing
Object, by the mixture carry out it is once sintered generate fluorine doped LiMn2O4 the step of specifically:
Fluoride and lithium carbonate, manganese source material and boric acid after the pulverization process is mixed to get the mixture；
The mixture is warming up to 700 DEG C~900 DEG C with the rate of 1~5 DEG C/min, keeps the temperature 12h~20h, then again with 1~
The rate of 5 DEG C/min is cooled to 300 DEG C, is cooled to room temperature, generates the LiMn2O4 of the fluorine doped.
Preferably, the molar ratio of the LiMn2O4 of the fluorine doped and the aluminium hydroxide is 1:0.05.
Preferably, the LiMn2O4 and aluminium hydroxide for weighing the fluorine doped in proportion carries out double sintering, described in generation
The step of manganate cathode material for lithium are as follows:
The LiMn2O4 of the fluorine doped and the aluminium hydroxide are warming up to 700 DEG C~900 DEG C with the rate of 1~5 DEG C/min, heat preservation
12h~20h；300 DEG C are cooled to the rate of 1~5 DEG C/min again, is cooled to room temperature, generates the manganate cathode material for lithium.
The present invention also provides a kind of manganate cathode material for lithium, by the preparation method system of manganate cathode material for lithium as the aforementioned
It is standby to form.
By doped fluoride in the present invention, the specific discharge capacity of LiMn2O4 can be significantly improved, it, will by double sintering
Aluminium hydroxide is coated on the LiMn2O4 surface of fluorine doped, can effectively improve the cycle performance of LiMn2O4, prepares high capacity Gao Xun
The manganate cathode material for lithium of ring；By addition cosolvent boric acid, fluoride can be made to become molten condition at a lower temperature,
It preferably penetrates into the lattice of LiMn2O4, the LiMn2O4 uniform doping of the fluorine doped of generation.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
It in addition, the technical solution between each embodiment of the present invention can be combined with each other, but must be general with this field
Based on logical technical staff can be realized, it will be understood that when the combination of technical solution appearance is conflicting or cannot achieve this
The combination of technical solution is not present, also not the present invention claims protection scope within.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
The present invention proposes a kind of preparation method of manganate cathode material for lithium, comprising the following steps:
Step S1, takes fluoride to do pulverization process；
Specifically, it takes fluoride to be put into pulverizer and does pulverization process, obtain the fluoride powder that median D50 is 1 ~ 2um.
Fluoride includes MgF2、AlF3、SiF4It is any one or more of.
By the way that fluoride powder is broken into fine grained, be conducive to the LiMn2O4 that fluorine is uniformly mixed to generation in subsequent step
In.
Fluoride and lithium carbonate, manganese source material and boric acid after pulverization process is mixed to get mixture by step S2,
The mixture is subjected to the once sintered LiMn2O4 for generating fluorine doped；
Specifically, fluoride and lithium carbonate, the manganese source material and boric acid after the pulverization process are mixed to get the mixing
Object.Wherein, the manganese source material includes one of manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide or a variety of.The mixing
The molar ratio of Li:Mn:F:B in object is 1:2:(0.02~0.1): 0.01.Boric acid becomes cosolvent during once sintered,
Fluoride can be made to become molten condition at a lower temperature, fluorine is penetrated into well in the lattice of LiMn2O4, it is real
Existing fluorine Uniform Doped.
The mixture is warming up to 700 DEG C~900 DEG C with the rate of 1 ~ 5 DEG C/min, keeps the temperature 12h~20h, then again with
The rate of 1 ~ 5 DEG C/min is cooled to 300 DEG C, is cooled to room temperature, generates the LiMn2O4 of the fluorine doped.
Step S3 weighs the LiMn2O4 and aluminium hydroxide of the fluorine doped, carries out double sintering, generates the lithium manganate cathode
The molar ratio of material, the LiMn2O4 of the fluorine doped and the aluminium hydroxide is 1:0.02 ~ 0.1.
Preferably, the LiMn2O4 of the fluorine doped and nano-grade aluminum hydroxide can be that 1:0.05 carries out secondary burning with molar ratio
Knot.The LiMn2O4 of fluorine doped and nano-grade aluminum hydroxide are warming up to 700 DEG C~900 DEG C with the rate of 1 ~ 5 DEG C/min, and heat preservation 12h~
20h；300 DEG C are cooled to the rate of 1 ~ 5 DEG C/min again, is cooled to room temperature, generates the manganate cathode material for lithium.
By doped fluoride, the specific discharge capacity of LiMn2O4 can be significantly improved, but the circulation of LiMn2O4 can be reduced
Aluminium hydroxide is coated on the LiMn2O4 surface of fluorine doped, can effectively improve the cyclicity of LiMn2O4 by performance by double sintering
Can, prepare the manganate cathode material for lithium of high capacity high circulation.
The present invention also provides having given a kind of positive electrode, the positive electrode by manganate cathode material for lithium as the aforementioned system
Preparation Method is prepared.
It is specifically described below by way of preparation method of the specific embodiment to manganate cathode material for lithium proposed by the present invention:
Embodiment 1
Weigh 0.61gMgF2, D50=1 ~ 2um is crushed to pulverizer；37gLi is weighed respectively2CO3、174gMnO2With
0.62gH3BO3, with the MgF after pulverization process2Uniformly mixing is carried out once sintered by following system: with the rate liter of 2 DEG C/min
For temperature to 700 DEG C, heat preservation 20h cools to room temperature with the furnace after being then cooled to 300 DEG C again with the rate of 2 DEG C/min, obtains fluorine doped
LiMn2O4.Weigh 3.9gAl (OH)3, with the LiMn of high efficient horizontal fusion machine and fluorine doped2O4After evenly mixing, by following system
It carries out double sintering: being warming up to 700 DEG C with the rate of 2 DEG C/min, keep the temperature 20h, be then cooled to again with the rate of 2 DEG C/min
After 300 DEG C, room temperature is cooled to the furnace, generate the manganate cathode material for lithium.
Manganate cathode material for lithium prepared by the present embodiment, acetylene black, graphite and binder in mass ratio 80: 5: 5: 10
Above-mentioned material stirring pulp is coated on aluminium foil, then with n-methyl-2-pyrrolidone (NMP) for binder 120 by mixing
Dry 12h obtains pole piece in DEG C vacuum oven.In the present embodiment, binder is Kynoar (PVDF).
Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, using Celgard2400 as diaphragm, with 1mol/L
LiPF6, ethylene carbonate (EC) and dimethyl carbonate (DMC) be electrolyte, wherein ethylene carbonate (EC) and dimethyl carbonate
(DMC) volume ratio is 1: 1.It is assembled into CR2025 type button cell in the glove box full of argon gas, which is carried out
Electrochemical property test.Specifically used LAND battery test system, the button cell carry out electrification at 3.0-4.3V, 1C multiplying power
Learn performance test.
Test result shows that in charge and discharge blanking voltage be 3.0-4.3V, under conditions of charge-discharge magnification is 1C, the mangaic acid
The first discharge specific capacity of lithium anode material is 128mAh/g, and the capacity retention ratio that circulation is 300 times is up to 81%.
Embodiment 2
Weigh 1.68gAlF3, it is crushed to D50=1 ~ 2um with pulverizer, weighs 37gLi respectively2CO3、158gMn2O3With
0.62gH3BO3, with the AlF after pulverization process3Uniformly mixing is carried out once sintered by following system: with the rate liter of 2 DEG C/min
For temperature to 800 DEG C, heat preservation 16h cools to room temperature with the furnace after being then cooled to 300 DEG C again with the rate of 2 DEG C/min, obtains fluorine doped
LiMn2O4.Weigh 3.9gAl (OH)3, with the LiMn of high efficient horizontal fusion machine and fluorine doped2O4After evenly mixing, by following system
It carries out double sintering: being warming up to 800 DEG C with the rate of 2 DEG C/min, keep the temperature 16h, be then cooled to again with the rate of 2 DEG C/min
After 300 DEG C, room temperature is cooled to the furnace, generate the manganate cathode material for lithium.
Manganate cathode material for lithium prepared by the present embodiment, acetylene black, graphite and binder in mass ratio 80: 5: 5: 10
Above-mentioned material stirring pulp is coated in aluminium foil upper with n-methyl-2-pyrrolidone (NMP) for binder by mixing, then
Dry 12h obtains pole piece in 120 DEG C of vacuum ovens.In the present embodiment, binder is Kynoar (PVDF).
Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, using Celgard2400 as diaphragm, with 1mol/L
LiPF6, ethylene carbonate (EC) and dimethyl carbonate (DMC) be electrolyte, wherein ethylene carbonate (EC) and dimethyl carbonate
(DMC) volume ratio is 1: 1.It is assembled into CR2025 type button cell in the glove box full of argon gas, which is carried out
Electrochemical property test.Specifically used LAND battery test system, the button cell carry out electrification at 3.0-4.3V, 1C multiplying power
Learn performance test.
Test result shows that in charge and discharge blanking voltage be 3.0-4.3V, under conditions of charge-discharge magnification is 1C, the mangaic acid
The first discharge specific capacity of lithium anode material is 134mAh/g, and the capacity retention ratio that circulation is 300 times is up to 84%.
Embodiment 3
Weigh 2.6gSiF4, it is crushed to D50=1 ~ 2um with pulverizer, weighs 37gLi respectively2CO3、153gMn3O4With
0.62gH3BO3, with the SiF after pulverization process4Uniformly mixing is carried out once sintered by following system: with the rate liter of 2 DEG C/min
For temperature to 900 DEG C, heat preservation 12h cools to room temperature with the furnace after being then cooled to 300 DEG C again with the rate of 2 DEG C/min, obtains fluorine doped
LiMn2O4.Weigh 7.8gAl (OH)3, with the LiMn of high efficient horizontal fusion machine and fluorine doped2O4After evenly mixing, by following system
It carries out double sintering: being warming up to 900 DEG C with the rate of 2 DEG C/min, keep the temperature 12h, be then cooled to again with the rate of 2 DEG C/min
After 300 DEG C, room temperature is cooled to the furnace, generate the manganate cathode material for lithium.
Manganate cathode material for lithium prepared by the present embodiment, acetylene black, graphite and binder in mass ratio 80: 5: 5: 10
Above-mentioned material stirring pulp is coated on aluminium foil, then with n-methyl-2-pyrrolidone (NMP) for binder 120 by mixing
Dry 12h obtains pole piece in DEG C vacuum oven.In the present embodiment, binder is Kynoar (PVDF).
Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, using Celgard2400 as diaphragm, with 1mol/L
LiPF6, ethylene carbonate (EC) and dimethyl carbonate (DMC) be electrolyte, wherein ethylene carbonate (EC) and dimethyl carbonate
(DMC) volume ratio is 1: 1.It is assembled into CR2025 type button cell in the glove box full of argon gas, electrochemistry is carried out to material
It can test.Specifically used LAND battery test system, the button cell carry out chemical property survey at 3.0-4.3V, 1C multiplying power
Examination.
Test result shows that in charge and discharge blanking voltage be 3.0-4.3V, under conditions of charge-discharge magnification is 1C, the mangaic acid
The first discharge specific capacity of lithium anode material is 137mAh/g, and the capacity retention ratio that circulation is 300 times is up to 80%.
Embodiment 4
Weigh 1.4gAlF3, it is crushed to D50=1 ~ 2um with pulverizer, weighs 37gLi respectively2CO3、153gMn3O4With
0.62gH3BO3, with the AlF after pulverization process3Uniformly mixing is carried out once sintered by following system: with the rate liter of 2 DEG C/min
For temperature to 850 DEG C, heat preservation 14h cools to room temperature with the furnace after being then cooled to 300 DEG C again with the rate of 2 DEG C/min, obtains primary
The LiMn of sintered fluorine doped2O4.Weigh 1.56gAl (OH)3, with the LiMn of high efficient horizontal fusion machine and fluorine doped2O4Uniformly mixing
Afterwards, double sintering is carried out by following system: being warming up to 850 DEG C with the rate of 2 DEG C/min, 14h is kept the temperature, then again with 2 DEG C/min
Rate be cooled to 300 DEG C after, cool to room temperature with the furnace, generate the manganate cathode material for lithium.
Manganate cathode material for lithium prepared by the present embodiment, acetylene black, graphite and binder in mass ratio 80: 5: 5: 10
Above-mentioned material stirring pulp is coated on aluminium foil, then with n-methyl-2-pyrrolidone (NMP) for binder 120 by mixing
Dry 12h obtains pole piece in DEG C vacuum oven.In the present embodiment, binder is Kynoar (PVDF).
Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, using Celgard2400 as diaphragm, with 1mol/L
LiPF6, ethylene carbonate (EC) and dimethyl carbonate (DMC) be electrolyte, wherein ethylene carbonate (EC) and dimethyl carbonate
(DMC) volume ratio is 1: 1.It is assembled into CR2025 type button cell in the glove box full of argon gas, which is carried out
Electrochemical property test.Specifically used LAND battery test system, the button cell carry out electrification at 3.0-4.3V, 1C multiplying power
Learn performance test.
Test result shows that in charge and discharge blanking voltage be 3.0-4.3V, under conditions of charge-discharge magnification is 1C, the mangaic acid
The first discharge specific capacity of lithium anode material is 136mAh/g, and the capacity retention ratio that circulation is 300 times is up to 84%.
Embodiment 5
Weigh 2.44gMgF2, it is crushed to D50=1 ~ 2um with pulverizer, weighs 37gLi respectively2CO3、158gMn2O3With
0.62gH3BO3, with the MgF after pulverization process2Uniformly mixing is carried out once sintered by following system: with the rate liter of 2 DEG C/min
For temperature to 750 DEG C, heat preservation 18h cools to room temperature with the furnace after being then cooled to 300 DEG C again with the rate of 2 DEG C/min, obtains primary
The LiMn of sintered fluorine doped2O4.Weigh 3.9gAl (OH)3, with the LiMn of high efficient horizontal fusion machine and fluorine doped2O4Uniformly mixing
Afterwards, double sintering is carried out by following system:: 750 DEG C are warming up to the rate of 5 DEG C/min, 18h is kept the temperature, then again with 5 DEG C/min
Rate be cooled to 300 DEG C after, cool to room temperature with the furnace, generate the manganate cathode material for lithium.
Manganate cathode material for lithium prepared by the present embodiment, acetylene black, graphite and binder in mass ratio 80: 5: 5:
Above-mentioned material stirring pulp is coated on aluminium foil by 10 mixing with n-methyl-2-pyrrolidone (NMP) for binder, then
Dry 12h obtains pole piece in 120 DEG C of vacuum ovens.In the present embodiment, binder is Kynoar (PVDF).
Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, using Celgard2400 as diaphragm, with 1mol/L
LiPF6, ethylene carbonate (EC) and dimethyl carbonate (DMC) be electrolyte, wherein ethylene carbonate (EC) and dimethyl carbonate
(DMC) volume ratio is 1: 1.It is assembled into CR2025 type button cell in the glove box full of argon gas, which is carried out
Electrochemical property test.Specifically used LAND battery test system, the button cell carry out electrification at 3.0-4.3V, 1C multiplying power
Learn performance test.
Test result shows that in charge and discharge blanking voltage be 3.0-4.3V, under conditions of charge-discharge magnification is 1C, the mangaic acid
The first discharge specific capacity of lithium anode material is 138mAh/g, and the capacity retention ratio that circulation is 300 times is up to 82%.
Embodiment 6
Weigh 1.04gSiF4, it is crushed to D50=1 ~ 2um with pulverizer, weighs 37gLi respectively2CO3、174gMnO2With
0.62gH3BO3, uniformly mix, carried out by following system once sintered: with the rate of 2 DEG C/min with the SiF4 after pulverization process
800 DEG C are warming up to, heat preservation 16h cools to room temperature with the furnace after being then cooled to 300 DEG C again with the rate of 2 DEG C/min, obtains one
The LiMn of secondary sintered fluorine doped2O4.Weigh 3.9gAl (OH)3, with the LiMn of high efficient horizontal fusion machine and fluorine doped2O4Uniformly mixing
Afterwards, double sintering is carried out by following system:: 800 DEG C are warming up to the rate of 3 DEG C/min, 16h is kept the temperature, then again with 3 DEG C/min
Rate be cooled to 300 DEG C after, cool to room temperature with the furnace, generate the manganate cathode material for lithium.
Manganate cathode material for lithium prepared by the present embodiment, acetylene black, graphite and binder in mass ratio 80: 5: 5:
Above-mentioned material stirring pulp is coated on aluminium foil by 10 mixing with n-methyl-2-pyrrolidone (NMP) for binder, then
Dry 12h obtains pole piece in 120 DEG C of vacuum ovens.In the present embodiment, binder is Kynoar (PVDF).
Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, using Celgard2400 as diaphragm, with 1mol/L
LiPF6, ethylene carbonate (EC) and dimethyl carbonate (DMC) be electrolyte, wherein ethylene carbonate (EC) and dimethyl carbonate
(DMC) volume ratio is 1: 1.It is assembled into CR2025 type button cell in the glove box full of argon gas, which is carried out
Electrochemical property test.Specifically used LAND battery test system, the button cell carry out electrification at 3.0-4.3V, 1C multiplying power
Learn performance test.
Test result shows that in charge and discharge blanking voltage be 3.0-4.3V, under conditions of charge-discharge magnification is 1C, the mangaic acid
The first discharge specific capacity of lithium anode material is 135mAh/g, and the capacity retention ratio that circulation is 300 times is up to 85%.
Embodiment 7
Weigh 1.04gSiF4And 0.62gMgF2, it is crushed to D50=1 ~ 2um with pulverizer, weighs 37gLi respectively2CO3、
87gMnO2、79gMn2O3And 0.62gH3BO3, with the SiF after pulverization process4Uniformly mixing is carried out once sintered by following system:
800 DEG C are warming up to the rate of 4 DEG C/min, keeps the temperature 16h, it is cold with furnace after being then cooled to 300 DEG C again with the rate of 4 DEG C/min
But to room temperature, obtain it is once sintered after fluorine doped LiMn2O4.Weigh 3.9gAl (OH)3, machine and fluorine doped are merged with high efficient horizontal
LiMn2O4After evenly mixing, double sintering is carried out by following system:: 800 DEG C are warming up to the rate of 4 DEG C/min, heat preservation
16h cools to room temperature with the furnace after being then cooled to 300 DEG C again with the rate of 4 DEG C/min, generates the manganate cathode material for lithium.
Manganate cathode material for lithium prepared by the present embodiment, acetylene black, graphite and binder in mass ratio 80: 5: 5: 10
Above-mentioned material stirring pulp is coated on aluminium foil, then with n-methyl-2-pyrrolidone (NMP) for binder 120 by mixing
Dry 12h obtains pole piece in DEG C vacuum oven.In the present embodiment, binder is Kynoar (PVDF).
Using the above-mentioned pole piece prepared as anode, lithium piece is as cathode, using Celgard2400 as diaphragm, with 1mol/L
LiPF6, ethylene carbonate (EC) and dimethyl carbonate (DMC) be electrolyte, wherein ethylene carbonate (EC) and dimethyl carbonate
(DMC) volume ratio is 1: 1.It is assembled into CR2025 type button cell in the glove box full of argon gas, which is carried out
Electrochemical property test.Specifically used LAND battery test system, the button cell carry out electrification at 3.0-4.3V, 1C multiplying power
Learn performance test.
Test result shows that in charge and discharge blanking voltage be 3.0-4.3V, under conditions of charge-discharge magnification is 1C, the mangaic acid
The first discharge specific capacity of lithium anode material is 135mAh/g, and the capacity retention ratio that circulation is 300 times is up to 85%.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by description of the invention, or directly/it is used in other correlations indirectly
Technical field be included in scope of patent protection of the invention.
Claims (9)
1. a kind of preparation method of manganate cathode material for lithium, which comprises the following steps:
Fluoride is taken to do pulverization process；
Fluoride and lithium carbonate, manganese source material and boric acid after pulverization process is mixed to get mixture, by the mixture
Carry out the once sintered LiMn2O4 for generating fluorine doped；
The LiMn2O4 and aluminium hydroxide of the fluorine doped are weighed, double sintering is carried out, generates the manganate cathode material for lithium, it is described to mix
The molar ratio of the LiMn2O4 of fluorine and the aluminium hydroxide is 1:0.02 ~ 0.1.
2. the preparation method of manganate cathode material for lithium as described in claim 1, which is characterized in that the fluoride includes MgF2、
AlF3、SiF4It is any one or more of.
3. the preparation method of manganate cathode material for lithium as described in claim 1, which is characterized in that the fluorine after the pulverization process
The median of compound is 1 ~ 2um.
4. the preparation method of manganate cathode material for lithium as described in claim 1, which is characterized in that the manganese source material includes two
Manganese oxide, manganese sesquioxide managnic oxide, mangano-manganic oxide are any one or more of.
5. the preparation method of manganate cathode material for lithium as described in claim 1, which is characterized in that the Li in the mixture:
The molar ratio of Mn:F:B is 1:2:(0.02~0.1): 0.01.
6. the preparation method of manganate cathode material for lithium as described in claim 1, which is characterized in that it is described will be after pulverization process
Fluoride and lithium carbonate, manganese source material and boric acid are mixed to get mixture, and the mixture is carried out once sintered generation and is mixed
The step of LiMn2O4 of fluorine specifically:
Fluoride and lithium carbonate, manganese source material and boric acid after the pulverization process is mixed to get the mixture；
The mixture is warming up to 700 DEG C~900 DEG C with the rate of 1~5 DEG C/min, keeps the temperature 12h~20h, then again with 1~
The rate of 5 DEG C/min is cooled to 300 DEG C, is cooled to room temperature, generates the LiMn2O4 of the fluorine doped.
7. the preparation method of manganate cathode material for lithium as described in claim 1, which is characterized in that the LiMn2O4 of the fluorine doped and
The molar ratio of the aluminium hydroxide is 1:0.05.
8. the preparation method of manganate cathode material for lithium as claimed in claim 7, which is characterized in that it is described weigh in proportion it is described
The step of LiMn2O4 and aluminium hydroxide of fluorine doped carry out double sintering, generate the manganate cathode material for lithium are as follows:
The LiMn2O4 of the fluorine doped and the aluminium hydroxide are warming up to 700 DEG C~900 DEG C with the rate of 1~5 DEG C/min, heat preservation
12h~20h；300 DEG C are cooled to the rate of 1~5 DEG C/min again, is cooled to room temperature, generates the manganate cathode material for lithium.
9. a kind of manganate cathode material for lithium, which is characterized in that by lithium manganate cathode such as described in any item of the claim 1 to 8
The preparation method of material is prepared.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111003731A (en) * | 2019-11-22 | 2020-04-14 | 贵州唯特高新能源科技有限公司 | Method for improving cycle performance of lithium manganate positive electrode material by doping high-valence metal fluoride |
| CN111003730A (en) * | 2019-11-22 | 2020-04-14 | 贵州唯特高新能源科技有限公司 | Preparation method for improving high-temperature stability of lithium manganate positive electrode material |
| CN111342024A (en) * | 2020-03-16 | 2020-06-26 | 陕西海恩新材料有限责任公司 | Long-cycle lithium manganate positive electrode material and preparation method thereof |
| CN115241425A (en) * | 2022-07-01 | 2022-10-25 | 湖南顺隆新能源科技有限公司 | Lithium manganate positive electrode material and preparation method thereof |
| CN115241425B (en) * | 2022-07-01 | 2023-09-05 | 湖南顺隆新能源科技有限公司 | Lithium manganate positive electrode material and preparation method thereof |
| CN116514173A (en) * | 2023-04-28 | 2023-08-01 | 巴斯夫杉杉电池材料有限公司 | Lithium manganate positive electrode material and preparation method thereof |
| CN116514173B (en) * | 2023-04-28 | 2024-03-22 | 巴斯夫杉杉电池材料有限公司 | Lithium manganate positive electrode material and preparation method thereof |
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