CN110429268A - A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof - Google Patents
A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to technical field of lithium ion, and in particular to a kind of modified boron doping lithium-rich manganese-based anode material, and preparation method is further disclosed, and is used to prepare the application of lithium ion battery.Boron doped nickel cobalt manganese compounds precursors can be obtained by being dissolved in boron-containing compound as boron source in precipitant solution, then using the method for co-precipitation in the present invention, and boron doping lithium-rich manganese-based anode material finally can be obtained by high temperature sintering.Preparation method of the present invention is using boron-containing compound as boron source, utilize borate factor in precipitation with higher, and aqueous solution is in alkalinity, it can be coexisted well with precipitating reagent, so that whole system is only with simple coprecipitation method, not only boron can be made in the surface doping of the positive electrode, simultaneously in material internal also Uniform Doped boron, keep the performance that positive electrode is made more stable, the service life is longer, while significantly improving capacity, first effect, high rate performance and the cyclical stability of positive electrode.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of modified boron doping lithium-rich manganese-based anode material,
And preparation method is further disclosed, and be used to prepare the application of lithium ion battery.
Background technique
Lithium ion battery is a kind of secondary cell i.e. rechargeable battery, and it is past between a positive electrode and a negative electrode that it relies primarily on lithium ion
Multiple movement carrys out work.In charge and discharge process, Li+Insertion and deintercalation back and forth between two electrodes: and when charging, Li+Then from just
Pole deintercalation is embedded in cathode by electrolyte, cathode is made to be in lithium-rich state；It is then opposite when electric discharge.Lithium ion battery is from last century
Since the nineties come out, by the development of more than two decades, huge numbers of families have been come into.Lithium ion battery is because of its energy density
Height, Environmental compatibility is good, has extended cycle life, the advantage that self-discharge rate is low, has evolved into most common energy storage device, widely
It applies on portable electronic device, electric car, aerospace, generate electricity the fields such as base station, the vehicles.And with portable
Electronic product, electric car it is universal, people have higher requirement, high specific energy, high power, height to the performance of lithium ion battery
Energy density, high security, long-life, low cost are the developing direction of the following lithium ion battery.Traditional lithium ion battery is just
Pole material specific capacity is lower (< 200mAh/g), is the principal element for limiting battery specific energy, therefore, in order to develop high specific energy
Battery, it is felt to be desirable to find the positive electrode with more height ratio capacity.
Rich lithium material is due to gradually causing with high specific capacity (generally more than 250mAh/g) and operating voltage (4.8V)
The extensive concern of people, it is considered to be the most possible positive electrode for becoming next-generation high performance lithium ion battery.But
Know rich lithium material but there is the coulombic efficiencies for the first time low, multiplying power of preparation and cycle performance is poor and voltage attenuation is serious etc.
Problem also constrains its commercialized application to limit the performance of lithium ion battery.
In the prior art, the main method for improving rich lithium material chemical property is cladding and doping
(Adv.Mater.2012,24,1192-1196；Adv.Funct.Mater.2014,1-7).The most common method for coating is to use
Al(OH)3、Al2O3、TiO2、ZrO2Equal inert materials carry out surface cladding to rich lithium material, such as Electrochimica Acta
50 (2005) 4784-4791, Journal of Power Sources 159 (2006) 1334-1339, CN101764210A,
The scheme recorded in CN103441252A, these covering materials may generally function as the rich lithium material surface texture of protection, prevent material
The effect of material and electrolyte contacts and then generation side reaction, improves the first charge-discharge efficiency of rich lithium material to a certain extent
And cycle performance and security performance.And the most common doping method is to be carried out using transition-metal cation to rich lithium material
It is bulk phase-doped, such as richness disclosed in the documents such as Chinese patent CN101694876A, CN102881891A and CN102881894A
Lithium anode material.And it then discloses in Chinese patent CN103199229A using PO4 3-、MoO4 2-、SO4 2-、AlO2 -Equal polyanions
The rich lithium material of doping, the material have the characteristics that first charge discharge efficiency is high, specific capacity is high, good cycle.For another example, Peking University's summer
Determine state et al. (Adv.Funct.Mater.2014,1-7) to pass through in the oxygen place doped polyanion (BO of boron4 3-) can be effective
Extend the cycle performance of rich lithium material.
But but there is apparent defects for the boron doping method being currently known, one is most doping processes are to be based on
What the methods of collosol and gel carried out, be not suitable for industrialized production, development and popularization is caused to be significantly restrained；Second it is part
Method is to mix boron-containing compound after driving body before the synthesis, is doped through high temperature sintering, causes technical process cumbersome, and makes
It obtains boron in material and is mainly distributed on surface, there is a problem of that boron dispersion is uneven and doping effect is undesirable, and then influence material
The chemical property of material.
Therefore, develop that a kind of preparation process is simple and lithium ion battery boron doping type richness lithium with more height ratio capacity
Manganese-based anode material improves the performance of lithium ion battery and market development has positive meaning.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in a kind of modified boron doping lithium-rich manganese-based anode material is provided,
The positive electrode has higher specific capacity, multiplying power and cyclical stability, helps to improve the chemical property of lithium ion battery；
Second technical problem to be solved by this invention is to provide above-mentioned modified boron doping lithium-rich manganese-based anode material
Preparation method, this method have preparation process is simple, easy to operate, yield is high, and be made positive electrode inside boron doping it is equal
Even advantage.
In order to solve the above technical problems, a kind of preparation side of modified boron doping lithium-rich manganese-based anode material of the present invention
Method includes the following steps:
(1) it takes manganese salt compound, nickel salt compound and cobalt salt compound to be dissolved in deionized water, it is molten to obtain metal salt
Liquid；
(2) it takes precipitating reagent to be dissolved in deionized water, obtains precipitant solution；Boron-containing compound is taken to be dissolved in deionized water
In, obtain boron-containing compound solution；Alternatively,
(2 ') take precipitating reagent to be dissolved in deionized water, obtain precipitant solution, and be added into the precipitant solution
Boron-containing compound mixes, and obtains the precipitant solution of boron-containing compound；
(3) by above-mentioned metal salt solution, precipitant solution and boron-containing compound or metal salt solution and boron-containing compound
Precipitant solution mix, reacted in 50-60 DEG C, obtain washed suspension, filtering, dry, obtain boron doping nickel cobalt
Manganese presoma；
(4) gained presoma and lithium salts are mixed, through high temperature sintering to get required modified boron doping lithium-rich manganese-based anode material
Material.
Specifically, in the step (1):
The manganese salt compound includes at least one of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate；
The nickel salt compound includes at least one of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate；
The cobalt salt compound includes at least one of cobaltous sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
Specifically, controlling in the metal salt solution in the step (1), the concentration of metal ion is 0.5-2mol/L.
Specifically, in the step (2) and (2 '):
The precipitating reagent includes at least one of sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide；
The boron-containing compound includes at least one of boric acid, Boratex, potassium borate, ammonium borate；
The molar ratio of the boron-containing compound and the precipitating reagent is 0.1-5:100.
Specifically, the preparation method of the modification boron doping lithium-rich manganese-based anode material:
In the step (2) and (2 '), the molar concentration for controlling the precipitant solution is 0.5-4mol/L
In the step (2), the molar concentration for controlling the boron-containing compound solution is 0.01-0.1mol/L.
Specifically, further including the steps that adjusting the pH value of reaction system 7-13 in the step (3).
More specifically, molten by control metal salt in the step (3) when the precipitating reagent is sodium carbonate or potassium carbonate
Liquid and the rate of addition of precipitant solution make the pH value 7-9 of reaction system；When the precipitating reagent is sodium hydroxide or hydroxide
When potassium, make the pH value of reaction system in the step (3) by the rate of addition of control metal salt solution and precipitant solution
10-13。
Specifically, in the step (3), mixing speed 400-1500r/min, reaction time 8-36h；The washing
Step is deionized water washing.
Specifically, in the step (4):
The lithium salts includes at least one of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate or lithium carbonate；
Control Li in the presoma and lithium salts+Molar ratio be 1:1-1:2.
Specifically, the high temperature sintering step specifically includes: in the step (4) with the heating rate of 3-10 DEG C/min
It is warming up to 400-650 DEG C, keeps the temperature 3-12h；It then proceedes to be continuously heating to 700-1000 DEG C with the heating rate of 3-10 DEG C/min,
Keep the temperature 10-30h.
The invention also discloses the modification boron doping lithium-rich manganese-based anode materials being prepared by the method.
The invention also discloses the modification boron doping lithium-rich manganese-based anode materials to be used to prepare lithium ion cell electrode
And the purposes of lithium ion battery.
The preparation method of modified boron doping lithium-rich manganese-based anode material of the present invention, by using boron-containing compound as boron
Source is dissolved in precipitant solution, then boron doped nickel cobalt manganese compounds precursors can be obtained using the method for co-precipitation, most
Boron doping lithium-rich manganese-based anode material can be obtained by high temperature sintering afterwards.Preparation method of the present invention utilizes boron-containing compound
As boron source, using borate factor in precipitation with higher, and aqueous solution can coexist well with precipitating reagent, make in alkalinity
Whole system is obtained only with simple coprecipitation method, not only boron can be made in the surface doping of the positive electrode, while
Material internal also Uniform Doped boron keeps the performance that positive electrode is made more stable, and the service life is longer, while significantly improving just
The capacity of pole material, first effect, high rate performance and cyclical stability.
Of the present invention preparation method is simple, easy to operate, low in cost, products collection efficiency is high, not only simplifies boron-doping
Step and the effect for improving boron-doping, and can significantly promote capacity, multiplying power and the cyclical stability of lithium-rich manganese base material
Etc. comprehensive performances, help to improve the chemical property of material, and result favorable reproducibility, be suitable for large-scale promotion, have it is excellent
Development prospect.
Modified boron doping lithium-rich manganese-based anode material is made in the present invention, and boron doping ratio is reasonable, so that the positive electrode
Obtain doping effect the most reasonable and material property, anode material for lithium-ion batteries obtained its discharge capacity, for the first time library
Human relations efficiency, multiplying power and cyclical stability significantly improve, and wherein discharge capacity is 292.7mAh/g, and coulombic efficiency is for the first time
88.5%, 1C multiplying power 244mAh/g, capacity keeps 88.9% after the circulations of 200 circles, effectively increases the electrification of lithium ion battery
Learn performance.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the electron microscope that the lithium-rich manganese-based presoma of boron doping is made in embodiment 1；
Fig. 2 is the charging and discharging curve for the first circle that boron doping lithium-rich manganese-based anode material is made in embodiment 1；
Fig. 3 is the high rate performance curve that boron doping lithium-rich manganese-based anode material is made in embodiment 1；
Fig. 4 is the cycle performance curve that boron doping lithium-rich manganese-based anode material is made in embodiment 1；
Fig. 5 is the charging and discharging curve for the first circle that boron doping lithium-rich manganese-based anode material is made in embodiment 4；
Fig. 6 is the high rate performance curve that boron doping lithium-rich manganese-based anode material is made in embodiment 4；
Fig. 7 is the cycle performance curve that boron doping lithium-rich manganese-based anode material is made in embodiment 4；
Fig. 8 is the first charge-discharge curve graph that lithium-rich manganese-based anode material is made in comparative example 1；
Fig. 9 is that the discharge capacity under lithium-rich manganese-based anode material different multiplying is made in comparative example 1；
Figure 10 is the cycle performance figure that lithium-rich manganese-based anode material is made in comparative example 1.
Specific embodiment
In the following embodiments of the present invention, for the confirming performance of modified boron doping lithium-rich manganese-based anode material obtained, with
The positive electrode is prepared into button cell, test performance includes discharge capacity, high rate performance, cycle performance；Specific button
Formula battery preparation step includes:
(1) lithium-rich manganese-based anode material obtained in each embodiment, conductive carbon black (Supper P) and Kynoar are taken
(PVDF) it is mixed in the ratio of 80:10:10, n-methyl-2-pyrrolidone (NMP) is added, slurry is made, be evenly applied to aluminium foil
On, the round pole piece that diameter is 1.4 centimetres is cut into after drying；
(2) it will be dried in 120 DEG C of vacuum oven after above-mentioned pole piece roll-in 12 hours, then in the hand for being full of argon gas
In casing, using pour lithium slice as negative electrode material, with 1mol/L LiPF6-EC+DEC+DMC (volume ratio 1:1:1) for electrolyte, with
Celgard2300 is diaphragm, dresses up CR2032 type button cell；
(3) the button experimental cell of assembling is subjected to charge-discharge test, the voltage model of charge and discharge on charge-discharge test instrument
It encloses are as follows: 2~4.8V, the current density for defining 200mA/g is 1C；High rate performance test charge and discharge system are as follows: successively with 0.1C,
The current density constant current charge-discharge of 0.2C, 0.5C, 1C, 3C each 3 weeks；The charge and discharge system of cycle performance test is: first in 2-
4.8V voltage range was with current density constant current charge-discharge 3 weeks of 0.1C, then in 2-4.6V voltage range with the current density of 1C
Carry out constant current charge-discharge.
Embodiment 1
The present embodiment tells the preparation method of modified boron doping lithium-rich manganese-based anode material, specifically comprises the following steps:
(1) prepare metal salt solution: first according to molar ratio be 4:1:1 weigh Manganous sulfate monohydrate, six hydration nickel sulfate and
Cobalt monosulfate heptahydrate；It is then dissolved in prepare in deionized water and obtains the metal salt solution that concentration of metal ions is 2mol/L；
(2) it prepares precipitant solution: taking sodium carbonate to be dissolved in and be configured to molar concentration in deionized water as the molten of 2mol/L
Liquid；It adds Boratex, stirs to being completely dissolved, boracic precipitant solution can be obtained, wherein Boratex and sodium carbonate rub
You are than being 2:100；
(3) it prepares boron doping nickel cobalt manganese carbonate precursor: under 750r/min stirring condition, by metal salt solution and sinking
Shallow lake agent solution is added dropwise in 200mL deionized water, so that reaction system is kept pH value 8 by controlling rate of addition, and control
Reaction system processed reacts 30h under the conditions of 55 DEG C, and the presoma reacted is washed with deionized, using suction filtration, drying
Boron doped nickel cobalt manganese compounds precursors (Mn can be prepared4/6Ni1/6Co1/6)CO3；
(4) it prepares boron doping lithium-rich manganese-based anode material: boron doped nickel cobalt manganese compounds precursors is pressed with lithium carbonate
The molar ratio of 1:0.85 uniformly mixes, and is subsequently placed in Muffle furnace and is warming up to 500 DEG C with the heating rate of 5 DEG C/min, using
The pre-burning of 5h；Continue to be warming up to 850 DEG C with the heating rate of 5 DEG C/min, is sintered 20h, being slowly cooled to room temperature can be prepared into
To boron doping lithium-rich manganese-based anode material.
Fig. 1 is the scanning electron microscopic picture of presoma manufactured in the present embodiment.
The lithium-rich manganese-based anode material that the present embodiment obtains is assembled into R2032 type button half-cell according to preceding method,
Fig. 2 is first charge-discharge curve graph under conditions of 25 DEG C, 2.0-4.8V, 1/10C, it is known that its discharge capacity for the first time
292.7mAh/g, coulombic efficiency is 88.5% for the first time；Fig. 3 is the discharge capacity under different multiplying, it is known that the electric discharge under 1C multiplying power
Capacity is 244mAh/g；Capacity known to Fig. 4 after 200 circle of 2.0-4.6V, 1C circulation keeps 88.9%.
Embodiment 2
The preparation method of modified boron doping lithium-rich manganese-based anode material, specifically comprises the following steps: described in the present embodiment
(1) prepare metal salt solution: first according to molar ratio be 4:1:1 weigh four nitric hydrate manganese, Nickelous nitrate hexahydrate and
Cabaltous nitrate hexahydrate is then dissolved in preparation in deionized water and obtains the metal salt solution of molar concentration 1mol/L；
(2) prepare precipitant solution: it is the molten of 1mol/L that potassium carbonate, which is dissolved in, and is configured to molar concentration in deionized water
Liquid；Boric acid is added, stirs to being completely dissolved, precipitant solution can be obtained；Wherein, the molar ratio of boric acid and precipitating reagent is
0.5:100；
(3) boron doped nickel cobalt manganese carbonate precursor is prepared: under 1000r/min stirring condition, by metal salt solution
It is added dropwise in 200mL deionized water with precipitant solution, so that reaction system is kept pH value by controlling rate of addition
7.5,15h then is reacted under the conditions of 50 DEG C, the presoma reacted is washed with deionized, and is using suction filtration, drying
Boron doped nickel cobalt manganese compounds precursors can be prepared；
(4) it prepares boron doping lithium-rich manganese-based anode material: boron doped nickel cobalt manganese compounds precursors is pressed with lithium nitrate
1:2 molar ratio uniformly mixes, and is subsequently placed in Muffle furnace and is warming up to 400 DEG C with the heating rate of 3 DEG C/min, using the pre- of 3h
It burns；Continue to be warming up to 900 DEG C with the heating rate of 3 DEG C/min, is sintered 12h, boron can be prepared by, which being slowly cooled to room temperature, mixes
Miscellaneous lithium-rich manganese-based anode material.
The lithium-rich manganese-based anode material of acquisition is assembled into R2032 type button half-cell according to preceding method, 25 DEG C,
Discharge capacity 272.6mAh/g for the first time under conditions of 2.0-4.8V, 1/10C, coulombic efficiency is under 84.3%, 1C multiplying power for the first time
Discharge capacity be 231.5mAh/g, 2.0-4.6V, 1C circulation 200 circle after capacity keep 92.8%.
Embodiment 3
The preparation method of modified boron doping lithium-rich manganese-based anode material, specifically comprises the following steps: described in the present embodiment
(1) prepare metal salt solution: first according to molar ratio be 5:2:1 weigh four chloride hydrate manganese, Nickel dichloride hexahydrate and
Cobalt chloride hexahydrate；It is then dissolved in the metal salt solution that 2mol/L is prepared in deionized water；
(2) prepare precipitant solution: it is 4mol/L's that potassium hydroxide, which is dissolved in, and is configured to molar concentration in deionized water
Solution；Ammonium borate is dissolved in the solution for being configured to that molar concentration is 0.2mol/L in deionized water；Wherein, ammonium borate and precipitating
The molar ratio of agent is 5:100；
(3) boron doped nickel cobalt manganese presoma is prepared: under 600r/min stirring condition, by metal salt solution, precipitating reagent
Solution and ammoniumborate solution are added dropwise in 200mL deionized water, so that reaction system is kept pH value by controlling rate of addition
It is 11, is then reacted under the conditions of 70 DEG C for 24 hours, reaction obtains presoma and is washed with deionized, using suction filtration, drying
Boron doped nickel cobalt manganese compounds precursors are prepared；
(4) boron doping lithium-rich manganese-based anode material is prepared: by boron doped nickel cobalt manganese compounds precursors and lithium hydroxide
It uniformly mixes, is subsequently placed in Muffle furnace with the heating rate of 5 DEG C/min from room temperature to 550 DEG C according to 1:1 molar ratio, then
By the pre-burning of 5h；Continue to be warming up to 700 DEG C with the heating rate of 5 DEG C/min, is sintered 15h, being slowly cooled to room temperature can make
It is standby to obtain boron doping lithium-rich manganese-based anode material.
The lithium-rich manganese-based anode material of acquisition is assembled into R2032 type button half-cell according to preceding method, 25 DEG C,
Discharge capacity 285.2mAh/g for the first time under conditions of 2.0-4.8V, 1/10C, coulombic efficiency is under 88.7%, 1C multiplying power for the first time
Discharge capacity be 238.4mAh/g；Capacity after 200 circle of 2.0-4.6V, 1C circulation keeps 84.1%.
Embodiment 4
The preparation method of modified boron doping lithium-rich manganese-based anode material, specifically comprises the following steps: described in the present embodiment
(1) prepare metal salt solution: first according to molar ratio be 6:3:1 weigh four acetate hydrate manganese, nickel acetate tetrahydrate and
Four water cobalt acetates；It is then dissolved in the metal salt solution that 0.5mol/L is prepared in deionized water；
(2) prepare precipitant solution: it is 1mol/L's that sodium hydroxide, which is dissolved in, and is configured to molar concentration in deionized water
Solution；Boric acid is added, stirs to being completely dissolved, precipitant solution can be obtained；Wherein, the molar ratio of boric acid and precipitating reagent is
4:100；
(3) boron doped nickel cobalt manganese presoma is prepared: under 1500r/min stirring condition, by metal salt solution and precipitating
Agent solution is added dropwise in 200mL deionized water, so that reaction system is kept pH value 13 by controlling rate of addition, is then existed
30h is reacted under the conditions of 60 DEG C, reaction obtains presoma and is washed with deionized, and boron can be prepared using suction filtration, drying
The nickel cobalt manganese compounds precursors of doping；
(4) it prepares boron doping lithium-rich manganese-based anode material: boron doped nickel cobalt manganese compounds precursors is pressed with lithium acetate
1:1.5 molar ratio uniformly mixes, and is subsequently placed in Muffle furnace with the heating rate of 10 DEG C/min from room temperature to 500 DEG C,
Using the pre-burning of 5h；Continue to be warming up to 1000 DEG C with the heating rate of 10 DEG C/min, is sintered 8h, is slowly cooled to room temperature
Boron doping lithium-rich manganese-based anode material is prepared.
The lithium-rich manganese-based anode material of acquisition is assembled into R2032 type button half-cell according to preceding method, Fig. 5 is 25
DEG C, the first charge-discharge curve graph under conditions of 2.0-4.8V, 1/10C, it is known that its discharge capacity 271.9mAh/g for the first time, for the first time
Coulombic efficiency is 91.8%；Fig. 6 is the discharge capacity under different multiplying, it is known that the discharge capacity under 1C multiplying power is 227mAh/g；
Capacity known to Fig. 7 after 200 circle of 2.0-4.6V, 1C circulation keeps 93.4%.
Embodiment 5
The present embodiment tells the preparation method of modified boron doping lithium-rich manganese-based anode material, specifically comprises the following steps:
(1) prepare metal salt solution: first according to molar ratio be 4:1:1 weigh Manganous sulfate monohydrate, six hydration nickel sulfate and
Cobalt monosulfate heptahydrate；It is then dissolved in prepare in deionized water and obtains the metal salt solution that concentration of metal ions is 1mol/L；
(2) it prepares precipitant solution: taking sodium carbonate to be dissolved in and be configured to molar concentration in deionized water as 0.5mol/L's
Solution；It adds potassium borate, stirs to being completely dissolved, boracic precipitant solution can be obtained, wherein Boratex and sodium carbonate
Molar ratio is 0.1:100；
(3) it prepares boron doping nickel cobalt manganese carbonate precursor: under 750r/min stirring condition, by metal salt solution and sinking
Shallow lake agent solution is added dropwise in 200mL deionized water, so that reaction system is kept pH value 8 by controlling rate of addition, and control
Reaction system processed reacts 30h under the conditions of 55 DEG C, and the presoma reacted is washed with deionized, using suction filtration, drying
Boron doped nickel cobalt manganese compounds precursors can be prepared；
(4) it prepares boron doping lithium-rich manganese-based anode material: boron doped nickel cobalt manganese compounds precursors is pressed with lithium ethoxide
The molar ratio of 1:1 uniformly mixes, and is subsequently placed in Muffle furnace and is warming up to 650 DEG C with the heating rate of 5 DEG C/min, using 5h's
Pre-burning；Continue to be warming up to 850 DEG C with the heating rate of 5 DEG C/min, is sintered 20h, boron can be prepared by being slowly cooled to room temperature
Adulterate lithium-rich manganese-based anode material.
Comparative example 1
The preparation method is the same as that of Example 1 for the present embodiment positive electrode, and difference is only that mixing without boron-containing compound
Lithium-rich manganese-based anode material is made in miscellaneous process.
The lithium-rich manganese-based anode material that the present embodiment obtains is assembled into R2032 type button half-cell according to preceding method.
Fig. 8 is first charge-discharge curve graph under conditions of 25 DEG C, 2.0-4.8V, 1/10C, it is known that its discharge capacity for the first time
251.2mAh/g, coulombic efficiency is 76.6% for the first time；Fig. 9 is the discharge capacity under different multiplying, the discharge capacity under 1C multiplying power
For 190.9mAh/g；Figure 10 is the cycle performance figure in 2.0-4.6V, 1C circulation, and the capacity after 200 circle of circulation keeps 72.9%.
From the point of view of above-mentioned charge-discharge test result, compared with the lithium-rich manganese-based anode material for being free of B doping in comparative example 1,
Discharge capacity, first charge discharge efficiency, high rate performance and the cycle performance that modified boron doping lithium-rich manganese base material is made in the method for the present invention are equal
It is very excellent.Modified boron doping richness lithium material specific capacity of the present invention is high, and high rate performance and good cycle can be used as pure
The power lithium-ion battery positive electrode of electric car, plug-in hybrid-power automobile.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of modified boron doping lithium-rich manganese-based anode material, which comprises the steps of:
(1) it takes manganese salt compound, nickel salt compound and cobalt salt compound to be dissolved in deionized water, obtains metal salt solution；
(2) it takes precipitating reagent to be dissolved in deionized water, obtains precipitant solution；Boron-containing compound is taken to be dissolved in deionized water,
Obtain boron-containing compound solution；Alternatively,
(2 ') take precipitating reagent to be dissolved in deionized water, obtain precipitant solution, and boracic is added into the precipitant solution
Compound mixes, and obtains the precipitant solution of boron-containing compound；
(3) by the heavy of above-mentioned metal salt solution, precipitant solution and boron-containing compound or metal salt solution and boron-containing compound
Shallow lake agent solution mixes, and is reacted in 50-60 DEG C, washed suspension, filtering, drying is obtained, before obtaining boron doping nickel cobalt manganese
Drive body；
(4) gained presoma and lithium salts are mixed, through high temperature sintering to get required modified boron doping lithium-rich manganese-based anode material.
2. the preparation method of modified boron doping lithium-rich manganese-based anode material according to claim 1, which is characterized in that described
In step (1):
The manganese salt compound includes at least one of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate；
The nickel salt compound includes at least one of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate；
The cobalt salt compound includes at least one of cobaltous sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
3. the preparation method of modified boron doping lithium-rich manganese-based anode material according to claim 1 or 2, which is characterized in that
It in the step (1), controls in the metal salt solution, the concentration of metal ion is 0.5-2mol/L.
4. the preparation method of modified boron doping lithium-rich manganese-based anode material according to claim 1-3, feature
It is, in the step (2) and (2 '):
The precipitating reagent includes at least one of sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide；
The boron-containing compound includes at least one of boric acid, Boratex, potassium borate, ammonium borate；
The molar ratio of the boron-containing compound and the precipitating reagent is 0.1-5:100.
5. the preparation method of modified boron doping lithium-rich manganese-based anode material according to claim 1-4, feature
It is:
In the step (2) and (2 '), the molar concentration for controlling the precipitant solution is 0.5-4mol/L
In the step (2), the molar concentration for controlling the boron-containing compound solution is 0.01-0.1mol/L.
6. the preparation method of modified boron doping lithium-rich manganese-based anode material according to claim 1-5, the step
Suddenly in (3), further include the steps that adjusting the pH value of reaction system 7-13.
7. the preparation method of modified boron doping lithium-rich manganese-based anode material according to claim 1-6, the step
Suddenly in (4):
The lithium salts includes at least one of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate or lithium carbonate；
Control Li in the presoma and lithium salts+Molar ratio be 1:1-1:2.
8. the preparation method of modified boron doping lithium-rich manganese-based anode material according to claim 1-7, the step
Suddenly in (4), the high temperature sintering step is specifically included: being warming up to 400-650 DEG C with the heating rate of 3-10 DEG C/min, is kept the temperature 3-
12h；It then proceedes to be continuously heating to 700-1000 DEG C with the heating rate of 3-10 DEG C/min, keeps the temperature 10-30h.
9. the modification boron doping lithium-rich manganese-based anode material being prepared by any one of claim 1-8 the method.
10. modified boron doping lithium-rich manganese-based anode material as claimed in claim 9 is used to prepare lithium ion cell electrode and lithium
The purposes of ion battery.
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