CN108987723A - A kind of preparation method of positive electrode, battery and its positive electrode - Google Patents
A kind of preparation method of positive electrode, battery and its positive electrode Download PDFInfo
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- CN108987723A CN108987723A CN201810922672.6A CN201810922672A CN108987723A CN 108987723 A CN108987723 A CN 108987723A CN 201810922672 A CN201810922672 A CN 201810922672A CN 108987723 A CN108987723 A CN 108987723A
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses the preparation method of a kind of positive electrode, battery and its positive electrode, which includes: lithium nickel cobalt dioxide layer (1) and Tungstenic compound layer (2)；Wherein, the Tungstenic compound layer (2) is coated on the surface of the lithium nickel cobalt dioxide layer (1), forms lithium nickel cobalt dioxide composite positive pole.The solution of the present invention can overcome in the prior art the defects of cyclical stability is poor, safety difference and service life is short, realize good cycling stability, the good and with long service life beneficial effect of safety.
Description
Technical field
The invention belongs to battery technology fields, especially belong to technical field of lithium batteries；More particularly to a kind of positive electrode, electricity
The preparation method more particularly to a kind of tungsten cladding lithium nickel cobalt dioxide positive electrode of pond and its positive electrode have the lithium nickel cobalt dioxide just
The preparation method of the lithium nickel cobalt dioxide positive electrode of the lithium nickel cobalt dioxide battery and lithium nickel cobalt dioxide battery of pole material.
Background technique
Lithium ion battery is with its high-energy-density, long circulation life, memory-less effect, safe and reliable and fast charging and discharging etc.
Advantage and become novel power supply technical research hot spot, be widely used in portable electronic product and new energy at present
On electric vehicle.This just needs lithium ion battery to have the features such as energy density is high, good cycling stability, security performance is excellent.
Lithium nickel cobalt dioxide positive electrode has the advantages that operating voltage is high, specific energy is big, but its cyclical stability is poor.With
Continuous improvement to battery energy density and electrical property demand, lithium nickel cobalt dioxide the cyclical stability and safety the problem of urgently
It solves.
In the prior art, the defects of that there are cyclical stabilities is poor, safety difference and service life is short.
Summary of the invention
It is an object of the present invention in view of the foregoing drawbacks, provide the preparation of a kind of positive electrode, battery and its positive electrode
Method, the cyclical stability to solve the problems, such as lithium nickel cobalt dioxide battery in the prior art is poor, reaches the effect for promoting cyclical stability
Fruit.
The present invention provides a kind of positive electrode, comprising: lithium nickel cobalt dioxide layer and Tungstenic compound layer；Wherein, described to contain tungsten
Nitride layer is closed, the surface of the lithium nickel cobalt dioxide layer is coated on, forms lithium nickel cobalt dioxide composite positive pole.
Optionally, the lithium nickel cobalt dioxide layer and the Tungstenic compound layer, exist with core-shell structure.
Match with above-mentioned positive electrode, another aspect of the present invention provides a kind of battery, comprising: the anode slurry of the battery
Material, comprising: N-Methyl pyrrolidone, and the conductive agent, binder and such as right that are added in the N-Methyl pyrrolidone
It is required that positive electrode described in any one of 1-2.
Optionally, wherein the mass ratio of the positive electrode, the conductive agent and the binder is 92~97:2~4:
1~3；And/or the conductive agent: including: SP；And/or the binder, comprising: PVDF.
Match with above-mentioned battery, further aspect of the present invention provides the preparation of the positive electrode of the battery described in more than one
Method, comprising: step 1 prepares Tungstenic compound solution and precipitant solution；Step 2, will lithium nickel cobalt dioxide presoma be added described in
In Tungstenic compound solution, after setting mixing speed stirring the first setting duration, the composite solution of lithium nickel cobalt dioxide and tungsten is obtained；
Rate is added by setting, to the precipitant solution is added in the composite solution of the lithium nickel cobalt dioxide and tungsten, to the nickel cobalt acid
The composite solution of lithium and tungsten carries out precipitation process, obtains the solid composite of lithium nickel cobalt dioxide and tungsten；Step 3, by nickel cobalt acid
The solid composite and lithium source of lithium and tungsten, the processing for being roasted and being ground obtain with core-shell structure presence and surface layer are coated with
The lithium nickel cobalt dioxide composite positive pole of Tungstenic compound layer.
Optionally, wherein in step 1, prepare Tungstenic compound solution, comprising: Tungstenic compound is dissolved in water, is made
Required Tungstenic compound solution；The molar concentration of the Tungstenic compound solution is 0.05~2.5mol/L；And/or preparation is heavy
Shallow lake agent solution, comprising: precipitating reagent is dissolved in water, precipitant solution needed for being made；The molar concentration of the precipitant solution is
0.05~2.5mol/L；And/or in step 2, the lithium nickel cobalt dioxide presoma, comprising: LiNixCoyO2；Wherein, 0.3≤x
≤ 0.9,0.05≤y≤0.4；And/or the setting mixing speed, comprising: 100~500rpm；And/or first setting
Duration, comprising: 3-6h；And/or rate is added in the setting, comprising: 25~30mL/min；And/or in step 3, described
The molar ratio of the solid composite of lithium nickel cobalt dioxide and tungsten and the lithium source is 0.8~1.2:0.8~1.2；And/or in the nickel
In cobalt acid lithium composite positive pole, the Tungstenic compound accounts for the 1~5% of the mass fraction of the lithium nickel cobalt dioxide；And/or institute
State lithium source, comprising: one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate.
Optionally, wherein in step 1, the Tungstenic compound, comprising: ammonium tungstate or ammonium metatungstate；And/or
The precipitating reagent, comprising: the mixed solution or ammonium hydroxide of ammonium hydroxide and sodium hydroxide and the mixed solution of sodium carbonate；Wherein, in institute
In the mixed solution for stating ammonium hydroxide and sodium hydroxide, the molar ratio of ammonium hydroxide and sodium hydroxide is 1~20:25~100；And/or in institute
In the mixed solution for stating ammonium hydroxide and sodium carbonate, the molar ratio of ammonium hydroxide and sodium carbonate is 1~20:25~100；And/or in step 2
In, x takes 0.6 or 0.8, and/or, y takes 0.2 or 0.4；And/or in step 3, the roasting, comprising: in oxygen atmosphere furnace
In, after roasting 2~15h with 200~1000 DEG C of temperature condition；And/or the grinding, comprising: the mixed grinding in grinder
50~70min.
Optionally, wherein in step 2, precipitation process is carried out to the composite solution of the lithium nickel cobalt dioxide and tungsten, comprising:
After the tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten is deposited to lithium nickel cobalt dioxide surface, it is filtered, collects admittedly
Shape object, washing and drying process；And/or in step 3, the processing that is roasted and ground, comprising: first roast and grind afterwards
Processing, or the processing of first baking after grinding.
Optionally, wherein in step 2, precipitation process is carried out to the composite solution of the lithium nickel cobalt dioxide and tungsten, is also wrapped
It includes: after the tungsten ion by the composite solution of the lithium nickel cobalt dioxide and tungsten is deposited to lithium nickel cobalt dioxide surface, or carrying out
It is mixed after the tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten to be deposited to lithium nickel cobalt dioxide surface before the filtering
Object is closed, the second setting duration is stood；And/or in step 3, the processing for being roasted and being ground, further includes: in the roasting
Later, the processing being also cooled to room temperature；And/or after the grinding, the processing that is also crushed and be sieved.
Optionally, wherein the second setting duration, comprising: 50~70min；And/or the washing, comprising: to certainly
Tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten, which has been deposited to, to be collected into the mixture behind lithium nickel cobalt dioxide surface
Solid content is washed with deionized；And/or the drying, comprising: drying.
The solution of the present invention can be improved by coating one layer of Tungstenic compound positive electrode on the lithium nickel cobalt dioxide surface
The high rate performance and cycle life of single battery in use process.
Further, the solution of the present invention, by coating one layer of Tungstenic compound positive electrode on the lithium nickel cobalt dioxide surface, most
The Tungstenic compound isolation metallic nickel of outer layer is directly contacted with electrolyte, can effectively improve the stability and safety of battery.
Further, the solution of the present invention is coated on lithium nickel cobalt dioxide surface by making tungsten, completely cuts off the straight of Ni metal and electrolyte
Contact inhibits the side reaction between electrolyte and positive electrode, is conducive to the cyclical stability and the safety that improve material.
The solution of the present invention as a result, is made by coating one layer of Tungstenic compound positive electrode on the lithium nickel cobalt dioxide surface
Lithium nickel cobalt dioxide composite positive pole solves the problems, such as that the cyclical stability of lithium nickel cobalt dioxide battery in the prior art is poor, thus, overcome
The defect that cyclical stability is poor in the prior art, safety difference and service life are short, realize good cycling stability, safety it is good and
Beneficial effect with long service life.
Other features and advantages of the present invention will be illustrated in the following description, also, partly becomes from specification
It obtains it is clear that understand through the implementation of the invention.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of an embodiment of positive electrode of the invention.
In conjunction with attached drawing, appended drawing reference is as follows in the embodiment of the present invention:
1- lithium nickel cobalt dioxide layer；2- Tungstenic compound layer.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the specific embodiment of the invention and
Technical solution of the present invention is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
According to an embodiment of the invention, providing a kind of positive electrode, the one of positive electrode of the invention is real as shown in Figure 1
Apply the structural schematic diagram of example.The positive electrode may include: lithium nickel cobalt dioxide layer 1 and Tungstenic compound layer 2.
Wherein, the Tungstenic compound layer 2 is coated on the surface of the lithium nickel cobalt dioxide layer 1, and it is compound just to form lithium nickel cobalt dioxide
Pole material.
Such as: one layer of Tungstenic compound positive electrode is coated on the lithium nickel cobalt dioxide surface, improves monomer electricity in use process
The high rate performance and cycle life in pond, outermost Tungstenic compound isolation metallic nickel are directly contacted with electrolyte, can effectively be mentioned
The stability and safety of high battery.
Lithium nickel cobalt dioxide anode composite is formed by the surface for making Tungstenic compound layer be coated on the lithium nickel cobalt dioxide layer as a result,
The high rate performance and cyclical stability of battery can be improved in material, and safety is good.
Optionally, the lithium nickel cobalt dioxide layer 1 and the Tungstenic compound layer 2, exist with core-shell structure.
As a result, by having lithium nickel cobalt dioxide layer and Tungstenic compound layer with core-shell structure, nickel cobalt can be further promoted
The stability of integrated structure between sour lithium layer and Tungstenic compound layer, to be conducive to be promoted the stability and safety of battery.
In an optional embodiment, the present invention provides a kind of lithium nickel cobalt dioxide composite positive pole and preparation method thereof,
The lithium nickel cobalt dioxide surface coat one layer of Tungstenic compound positive electrode, improve use process in single battery high rate performance and
Cycle life, outermost Tungstenic compound isolation metallic nickel are directly contacted with electrolyte, can effectively improve the stability of battery
With safety；Preparation method is simple, it is easy to accomplish.
In an optional example, a kind of preparation method of lithium nickel cobalt dioxide composite positive pole of the invention may include
Following steps:
Tungstenic compound is dissolved in water and is configured to solution A (such as: Tungstenic compound solution) by step 1), by molar concentration
Count 0.05~2.5mol/L；Precipitating reagent is dissolved in water and is configured to B solution (such as: precipitant solution), is by molar concentration meter
0.05~2.5mol/L, the major function of precipitating reagent are that tungsten ion is deposited to lithium nickel cobalt dioxide surface.
Optionally, the Tungstenic compound be ammonium tungstate or ammonium metatungstate, account for the lithium nickel cobalt dioxide mass fraction 1~
5%.
Optionally, ammonium hydroxide and sodium hydroxide ratio are 1~20:100 by mol or the mixing of ammonium hydroxide and sodium carbonate is molten
Liquid, ammonium hydroxide and sodium carbonate ratio are 1~20:100 by mol.
The solution A is added in lithium nickel cobalt dioxide presoma by step 2), is placed in ball mill, and mixing speed is 100~
500rpm (such as: mixing speed can also be 200rpm, 300rpm, 400rpm etc.), B is added in ball milling mixing 3-6h thereto
Solution (such as: B solution is added with the rate of 25~30mL/min)；Wait react complete (such as: precipitating completely after stand 50~
70min, preferably 1h), solid content is collected in filtering, then it is washed, dry (such as: solid is washed with deionized water
Wash and dry), obtain A solid (such as: the solid composite of lithium nickel cobalt dioxide and tungsten).
Optionally, the lithium nickel cobalt dioxide presoma is LiNixCoyO2, based on molal weight, 0.3≤x≤0.9,0.05≤y
≤0.4；It is preferred that the molecular formula of lithium nickel cobalt dioxide presoma is LiNi0.8Co0.2O2Or LiNi0.6Co0.4O2。
Step 3) roasts the A solid and lithium source (such as: 1:1 is mixed in molar ratio) in oxygen atmosphere furnace high temperature,
Temperature be 200~1000 DEG C, the time be 2~15h, product after being roasted, be fully ground (such as: in grinder mixed grinding
50~70min, preferably 60min) after, obtain with existing for core-shell structure, surface layer be coated with Tungstenic compound layer nickel cobalt acid
Lithium composite positive pole.
Wherein, it high-temperature roasting and can also be cooled to room temperature after first mixed grinding again.
Optionally, the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate.
As it can be seen that the present invention provides a kind of preparation method of lithium nickel cobalt dioxide composite positive pole (such as: synthesis core shell structure
The method of the lithium nickel cobalt dioxide anode material for lithium-ion batteries of tungsten cladding), the preparation method is at low cost, and it is easy to operate, it can be in anode
Material surface is formed uniformly one layer of fast-ionic conductor clad.By the preparation method, can be made required lithium nickel cobalt dioxide lithium from
Sub- cell positive material effectively improves lithium ion in positive material so that lithium fast-ionic conductor has excellent ionic conductivity
Diffusion in material；Moreover, tungsten is coated on lithium nickel cobalt dioxide surface, Ni metal can be completely cut off and contacted with the direct of electrolyte, electricity is inhibited
The side reaction between liquid and positive electrode is solved, the cyclical stability and the safety that improve material are conducive to.
Below by several specific embodiments (such as embodiment 1, embodiment 2 and comparative example), to above-mentioned nickel cobalt of the invention
The specific operation process of step 2) and step 3) is more specifically illustrated in the preparation method of sour lithium composite positive pole.
Embodiment 1:
By 1.65kg lithium nickel cobalt dioxide presoma Ni0.8Co0.2(OH)2The reaction kettle that 1mol/L ammonium metatungstate solution is housed is added
In, it is stirred continuously, mixing speed 500rpm, adds the sodium hydroxide and ammonium hydroxide of 0.5mol/L into reaction kettle with 25mL/min
Mixed solution, ammonium hydroxide and sodium hydroxide ratio are 1:25 by mol, after precipitating reagent adds, are stood after precipitating completely
Solid is collected in 1h, filtering, and solid is washed and dried with deionized water.Then the solid of drying and lithium hydroxide are being ground
Machine mixed grinding 60min, 1:1 is mixed in molar ratio, then high-temperature roasting 15h under the conditions of 800 DEG C, after being cooled to room temperature, warp
It crushes, sieving obtains the cobalt nickel oxide aluminium lithium composite positive pole of surface cladding Tungstenic compound layer.
Embodiment 2:
By 1.23kg lithium nickel cobalt dioxide presoma Ni0.8Co0.2(OH)2The reaction kettle that 0.8mol/L ammonium tungstate solution is housed is added
In, it is stirred continuously, mixing speed 500rpm, adds 0.6mol/L sodium hydroxide and ammonium hydroxide into reaction kettle with 30mL/min
Mixed solution, ammonium hydroxide and sodium hydroxide ratio are 1:25 by mol, after precipitating reagent adds, stand 1h after precipitating completely,
Solid is collected in filtering, and solid is washed and dried with deionized water.Then by the solid of drying and lithium hydroxide in grinder
Mixed grinding 60min, 1:1 is mixed in molar ratio, then high-temperature roasting 15h under the conditions of 1000 DEG C, after being cooled to room temperature, through powder
Broken, sieving obtains the cobalt nickel oxide aluminium lithium composite positive pole of surface cladding Tungstenic compound layer.
Comparative example: directly by doping type lithium nickel cobalt dioxide presoma Ni0.8Co0.2(OH)2It is mixed with lithium hydroxide, in molar ratio
1:1 is in grinder mixed grinding 60min, in 800 DEG C of high-temperature roasting 15h, after being cooled to room temperature, is crushed, being sieved is aoxidized
Nickel cobalt aluminium lithium composite positive pole.
Contrast on effect:
Positive electrode that embodiment 1, embodiment 2, comparative example are obtained, SP (conductive agent), PVDF (binder) are according to matter
Ratio of the amount than 95:3:2 is added in NMP, is stirred evenly and is prepared into anode sizing agent, lithium piece, electrolyte, and diaphragm is assembled into button
Battery.
Embodiment 1, the specific capacity of embodiment 2 and comparative example, first charge discharge efficiency, the correlation data for recycling conservation rate, Ke Yican
The example being shown in Table 1.
1 embodiment of table and comparative example electrical property compare
As it can be seen that the preparation method preparation gained lithium nickel cobalt dioxide using above-mentioned lithium nickel cobalt dioxide composite positive pole of the invention is multiple
The battery of positive electrode is closed, specific capacity, first charge discharge efficiency and circulation volume conservation rate are superior to common batteries.
Through a large amount of verification experimental verification, using the technical solution of the present embodiment, by coating one layer on the lithium nickel cobalt dioxide surface
Tungstenic compound positive electrode, outermost Tungstenic compound isolation metallic nickel are directly contacted with electrolyte, can effectively improve electricity
The stability and safety in pond.
According to an embodiment of the invention, additionally providing a kind of battery corresponding to positive electrode.The anode sizing agent of the battery,
It may include: N-Methyl pyrrolidone, and the conductive agent, binder and the above institute that are added in the N-Methyl pyrrolidone
The positive electrode stated.
As a result,
Optionally, the mass ratio of the positive electrode, the conductive agent and the binder is 92~97:2~4:1~3
(preferably can be 95:3:2).
As a result,
Optionally, the conductive agent: may include: SP；And/or the binder, it may include: PVDF.
Such as: by above-described positive electrode, SP (conductive agent), PVDF (binder) according to mass ratio 95:3:2 ratio
Example is added in NMP, is stirred evenly and is prepared into anode sizing agent, lithium piece, electrolyte, and diaphragm is assembled into button cell.It is verified, it should
Specific capacity, first charge discharge efficiency and the circulation volume conservation rate of button cell have obtained corresponding promotion, may refer to example shown in table 1
Son.
As a result,
The processing and function realized by the battery of the present embodiment essentially correspond to aforementioned positive electrode shown in FIG. 1
Embodiment, principle and example, therefore not detailed place in the description of the present embodiment, may refer to mutually speaking on somebody's behalf in previous embodiment
Bright, this will not be repeated here.
Through a large amount of verification experimental verification, completely cut off using technical solution of the present invention by making tungsten be coated on lithium nickel cobalt dioxide surface
Ni metal is directly contacted with electrolyte, is inhibited the side reaction between electrolyte and positive electrode, is conducive to improve following for material
Ring stability and safety.
According to an embodiment of the invention, additionally providing a kind of preparation method of the positive electrode of battery corresponding to battery.
The preparation method of the positive electrode of the battery may include:
Step 1 prepares Tungstenic compound solution and precipitant solution.
Optionally, in step 1, Tungstenic compound solution is prepared, may include: that Tungstenic compound is dissolved in water, is made
Required Tungstenic compound solution, the molar concentration of the Tungstenic compound solution are 0.05~2.5mol/L.
Such as: Tungstenic compound is dissolved in water and is configured to solution A (such as: Tungstenic compound solution), by molar concentration meter
0.05~2.5mol/L.
As a result, by the way that Tungstenic compound and water to be configured to the Tungstenic compound solution of required molar concentration, preparation method
Simplicity, preparation gained Tungstenic compound solution are used as the lithium nickel cobalt dioxide anode composite material that preparation surface layer is coated with Tungstenic compound layer
The raw material of material is conducive to promotion and prepares the convenience of lithium nickel cobalt dioxide composite positive pole, and promotes lithium nickel cobalt dioxide anode composite material
The stability and safety of material.
More optionally, in step 1, the Tungstenic compound may include: ammonium tungstate or ammonium metatungstate.
As a result, by the Tungstenic compound of diversified forms, the flexibility and just of Tungstenic compound solution preparation can be promoted
Victory.
Optionally, in step 1, precipitant solution is prepared, may include: that precipitating reagent is dissolved in water, precipitating needed for being made
Agent solution, the molar concentration of the precipitant solution are 0.05~2.5mol/L.
Such as: precipitating reagent is dissolved in water and is configured to B solution (such as: precipitant solution), by molar concentration meter be 0.05~
2.5mol/L, the major function of precipitating reagent are that tungsten ion is deposited to lithium nickel cobalt dioxide surface.
As a result, by the way that precipitating reagent and water to be configured to the precipitant solution of required molar concentration, preparation method is easy, preparation
Gained precipitant solution is used as the medium that preparation surface layer is coated with the lithium nickel cobalt dioxide composite positive pole of Tungstenic compound layer, favorably
The reliability and high efficiency on lithium nickel cobalt dioxide surface are deposited in promotion Tungstenic compound layer.
More optionally, the precipitating reagent may include: the mixed solution or ammonium hydroxide and carbonic acid of ammonium hydroxide and sodium hydroxide
The mixed solution of sodium.
Wherein, in the mixed solution of the ammonium hydroxide and sodium hydroxide, the molar ratio of ammonium hydroxide and sodium hydroxide is 1~20:
25~100 (such as: the molar ratio of ammonium hydroxide and sodium hydroxide can be 10:80,5:95 etc.)；And/or in the ammonium hydroxide and carbonic acid
In the mixed solution of sodium, the molar ratio of ammonium hydroxide and sodium carbonate be 1~20:25~100 (such as: the molar ratio of ammonium hydroxide and sodium carbonate
It can be 5:75,15:90 etc.).
Such as: ammonium hydroxide and sodium hydroxide ratio are 1~20:100 by mol or the mixing of ammonium hydroxide and sodium carbonate is molten
Liquid, ammonium hydroxide and sodium carbonate ratio are 1~20:100 by mol.
As a result, by the precipitating reagent of diversified forms, the flexibility and convenience of Tungstenic compound preparation can be promoted.
Lithium nickel cobalt dioxide presoma is added in the Tungstenic compound solution step 2, by setting mixing speed stirring first
After setting duration, the composite solution of lithium nickel cobalt dioxide and tungsten is obtained.Rate is added by setting, to the compound of the lithium nickel cobalt dioxide and tungsten
The precipitant solution is added in solution, precipitation process is carried out to the composite solution of the lithium nickel cobalt dioxide and tungsten, obtains nickel cobalt acid
The solid composite of lithium and tungsten.
Optionally, in step 2, the lithium nickel cobalt dioxide presoma, may include: LiNixCoyO2.Wherein, 0.3≤x≤
0.9,0.05≤y≤0.4.
Such as: the lithium nickel cobalt dioxide presoma is LiNixCoyO2, based on molal weight, 0.3≤x≤0.9,0.05≤y≤
0.4。
The lithium nickel cobalt dioxide presoma for passing through diversified forms as a result, can promote the compound preparation of lithium nickel cobalt dioxide and tungsten
Flexibility and convenience.
More optionally, in step 2, x takes 0.6 or 0.8, and/or, y takes 0.2 or 0.4.
Such as: the molecular formula of preferred lithium nickel cobalt dioxide presoma is LiNi0.8Co0.2O2Or LiNi0.6Co0.4O2。
Pass through the lithium nickel cobalt dioxide presoma determined by preferred molecular formula as a result, it is ensured that lithium nickel cobalt dioxide and tungsten it is compound
The flexibility and convenience of object preparation, can also promote the stability and safety of the compound of lithium nickel cobalt dioxide and tungsten, Jin Eryou
Conducive to promotion battery performance.
Optionally, in step 2, the setting mixing speed, may include: 100~500rpm.
As a result, by being stirred by reasonable mixing speed to lithium nickel cobalt dioxide presoma and Tungstenic compound solution, one
Aspect can guarantee stirring uniformity and safety, on the other hand also help guarantee gained lithium nickel cobalt dioxide and tungsten it is compound molten
The stability and reliability of liquid.
Optionally, in step 2, the first setting duration, may include: 3-6h.
Pass through the reasonable stirring duration of setting as a result, it can be ensured that the uniformity of stirring, high reliablity；It may also be ensured that
It does not stir excessively, energy conservation, and can be to avoid because being damaged caused by excessively stirring the performance to the composite solution of lithium nickel cobalt dioxide and tungsten.
Optionally, in step 2, rate is added in the setting, may include: 25~30mL/min.
As a result, by being added precipitant solution into the composite solution of lithium nickel cobalt dioxide and tungsten so that rate is reasonably added, one
Aspect can guarantee the reliability and stability being added, and on the other hand can control Tungstenic compound and precipitate on lithium nickel cobalt dioxide surface
Efficiency and effect, thus be conducive to promoted gained lithium nickel cobalt dioxide and tungsten solid composite performance.
Optionally, in step 2, precipitation process is carried out to the composite solution of the lithium nickel cobalt dioxide and tungsten, may include: to
After tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten is deposited to lithium nickel cobalt dioxide surface, it is filtered, collects solid
Object, washing and drying process.
Such as: the solution A is added in lithium nickel cobalt dioxide presoma, is placed in ball mill, mixing speed is 100~500rpm
(such as: mixing speed can also be 200rpm, 300rpm, 400rpm etc.), B solution (example is added in ball milling mixing 3-6h thereto
Such as: B solution is added with the rate of 25~30mL/min)；Wait react complete (such as: precipitating completely after stand 50~70min, it is excellent
It is selected as 1h), solid content is collected in filtering, then it is washed, dry (such as: solid is washed and dried with deionized water
It is dry), obtain A solid (such as: the solid composite of lithium nickel cobalt dioxide and tungsten).
As a result, by being filtered after tungsten ion is deposited to lithium nickel cobalt dioxide surface, collecting solid content, washing and drying etc.
Processing, on the one hand ensure that completeness and reliability that tungsten ion precipitates on lithium nickel cobalt dioxide surface, on the other hand pass through filtering, receipts
The processing such as collection solid content, washing and drying can promote the quality and performance of the solid composite of gained lithium nickel cobalt dioxide and tungsten.
More optionally, the washing, may include: to from the tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten
The solid content being collected into mixture after being deposited to lithium nickel cobalt dioxide surface, is washed with deionized.
Solid content after being deposited to lithium nickel cobalt dioxide surface to tungsten ion by using deionized water as a result, is washed,
It can guarantee the clean-up performance of cleaning, it can also be ensured that tungsten ion will not be influenced because of cleaning and be deposited to lithium nickel cobalt dioxide surface
The quality and performance of solid content afterwards are conducive to the cyclical stability and the safety that promote final gained battery.
More optionally, the drying may include: drying.
It is dried by way of drying as a result, drying efficiency is high, and will not bring other impurity into, will not influence
Tungsten ion has been deposited to the quality and performance of solid content behind lithium nickel cobalt dioxide surface itself.
Further, in step 2, precipitation process is carried out to the composite solution of the lithium nickel cobalt dioxide and tungsten, can also wrapped
It includes: after the tungsten ion by the composite solution of the lithium nickel cobalt dioxide and tungsten is deposited to lithium nickel cobalt dioxide surface, or carrying out
It is mixed after the tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten to be deposited to lithium nickel cobalt dioxide surface before the filtering
Object is closed, the second setting duration is stood.
As a result, by stewing process after the completion of precipitating, the completeness and reliability of precipitating may further ensure that, in turn
Further promote the stability and safety of gained cycle performance of battery.
Wherein, the second setting duration, may include: 50~70min.
Duration is stood by the way that setting is reasonable as a result, it can be ensured that the completeness and reliability of precipitating can also promote system
Standby efficiency.
Step 3, by the solid composite and lithium source of the lithium nickel cobalt dioxide and tungsten, the processing for being roasted and being ground obtains
With core-shell structure presence and surface layer is coated with the lithium nickel cobalt dioxide composite positive pole of Tungstenic compound layer.
Such as: the preparation method is at low cost, easy to operate, can be formed uniformly one layer of fast-ionic conductor on positive electrode surface
Clad.By the preparation method, required lithium nickel cobalt dioxide anode material for lithium-ion batteries can be made, so that lithium fast-ionic conductor
With excellent ionic conductivity, diffusion of the lithium ion in positive electrode is effectively improved；Moreover, tungsten is coated on lithium nickel cobalt dioxide
Surface can completely cut off Ni metal and contact with the direct of electrolyte, inhibit the side reaction between electrolyte and positive electrode, be conducive to
Improve cyclical stability and the safety of material.
Lithium nickel cobalt dioxide anode composite is formed by the surface for making Tungstenic compound layer be coated on the lithium nickel cobalt dioxide layer as a result,
The high rate performance and cyclical stability of battery can be improved in material, and safety is good；Make lithium nickel cobalt dioxide layer and Tungstenic compound layer
Exist with core-shell structure, can further promote the stability of integrated structure between lithium nickel cobalt dioxide layer and Tungstenic compound layer, from
And be conducive to be promoted the stability and safety of battery.
Optionally, in step 3, the molar ratio of the solid composite of the lithium nickel cobalt dioxide and tungsten and the lithium source is 0.8
~1.2:0.8~1.2 (preferably 1:1).
As a result, by the way that the solid composite of lithium nickel cobalt dioxide and tungsten and the molar ratio of the lithium source is rationally arranged, it can be ensured that
The required quality and required performance of gained lithium nickel cobalt dioxide composite positive pole, to preferably ensure the stable circulation of gained battery
Property and safety.
Optionally, in step 3, in the lithium nickel cobalt dioxide composite positive pole, the Tungstenic compound accounts for the nickel
The 1~5% of the mass fraction of cobalt acid lithium.
Such as: the Tungstenic compound be ammonium tungstate or ammonium metatungstate, account for the lithium nickel cobalt dioxide mass fraction 1~
5%.
Pass through the content of Tungstenic compound in rationally setting lithium nickel cobalt dioxide composite positive pole as a result, it can be ensured that nickel cobalt
The performance of sour lithium composite positive pole thereby further ensures that the quality and performance of gained battery.
Optionally, in step 3, the lithium source, comprising: one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate
Or it is several.
As a result, by the lithium source of diversified forms, the flexibility and convenience of lithium source setting can be promoted, and then promotes nickel cobalt
The flexibility and convenience of sour lithium composite positive pole preparation, and the quality of gained battery and the available guarantee of performance.
Optionally, in step 3, the roasting may include: in oxygen atmosphere furnace, with 200~1000 DEG C of temperature
After condition roasts 2~15h.
As a result, by the way that the factors such as calcination atmosphere, temperature and time are rationally arranged, it can be ensured that roasting efficiency and effect, and
Energy conservation, safety.
Optionally, in step 3, the grinding may include: 50~70min of mixed grinding in grinder.
Such as: the A solid and lithium source (such as: 1:1 is mixed in molar ratio) are roasted, temperature in oxygen atmosphere furnace high temperature
Degree be 200~1000 DEG C, the time be 2~15h, product after being roasted, be fully ground (such as: in grinder mixed grinding 50
~70min, preferably 60min) after, obtain with existing for core-shell structure, surface layer be coated with the lithium nickel cobalt dioxide of Tungstenic compound layer
Composite positive pole.
Logical setting grinding duration as a result, it can be ensured that the fineness of grinding gained abrasive, and efficient, energy conservation, moreover it is possible to ensure
The quality and performance of gained abrasive will not be influenced because of grinding or excessive grinding not in place.
Optionally, in step 3, the processing for being roasted and being ground may include: the processing for first roasting and grinding afterwards, or
The processing of person elder generation baking after grinding.
Such as: it high-temperature roasting and can also be cooled to room temperature after first mixed grinding again.
As a result, by selecting the sequence of roasting and grinding according to use demand, so as to lithium nickel cobalt dioxide composite positive pole
Prepare it is more flexible, more convenient.
Further, in step 3, the processing for being roasted and being ground can also include: after the roasting, also
The processing being cooled to room temperature；And/or after the grinding, the processing that is also crushed and be sieved.
As a result, by the processing such as being cooled down, being crushed and is sieved, gained lithium nickel cobalt dioxide anode composite can be further promoted
The precision and stabilization and security performance of material.
The processing and function realized by the preparation method of the present embodiment essentially correspond to the embodiment of aforementioned battery, original
Reason and example, therefore not detailed place in the description of the present embodiment, may refer to the related description in previous embodiment, do not do herein
It repeats.
Contained using technical solution of the present invention by coating one layer on the lithium nickel cobalt dioxide surface through a large amount of verification experimental verification
Lithium nickel cobalt dioxide composite positive pole is made in tungsten compound positive electrode, and the circulation for solving lithium nickel cobalt dioxide battery in the prior art is steady
The problem of qualitative difference, thus, overcome in the prior art the defect that cyclical stability is poor, safety difference and service life are short, realizes
Good cycling stability, the good and with long service life beneficial effect of safety.
To sum up, it will be readily appreciated by those skilled in the art that under the premise of not conflicting, above-mentioned each advantageous manner can be certainly
It combined, be superimposed by ground.
The above description is only an embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should be included within scope of the presently claimed invention.
Claims (10)
1. a kind of positive electrode characterized by comprising lithium nickel cobalt dioxide layer (1) and Tungstenic compound layer (2)；Wherein,
The Tungstenic compound layer (2) is coated on the surface of the lithium nickel cobalt dioxide layer (1), forms lithium nickel cobalt dioxide anode composite material
Material.
2. positive electrode according to claim 1, which is characterized in that the lithium nickel cobalt dioxide layer (1) and the tungstenic chemical combination
Nitride layer (2), exists with core-shell structure.
3. a kind of battery, which is characterized in that the anode sizing agent of the battery, comprising: N-Methyl pyrrolidone, and it is added to institute
State conductive agent, binder and such as positive electrode of any of claims 1-2 in N-Methyl pyrrolidone.
4. battery according to claim 3, which is characterized in that wherein,
The mass ratio of the positive electrode, the conductive agent and the binder is 92~97:2~4:1~3；
And/or
The conductive agent: including: SP；And/or
The binder, comprising: PVDF.
5. a kind of preparation method of the positive electrode of the battery as described in any one of claim 3-4, which is characterized in that packet
It includes:
Step 1 prepares Tungstenic compound solution and precipitant solution；
Lithium nickel cobalt dioxide presoma is added in the Tungstenic compound solution step 2, by the first setting of stirring of setting mixing speed
After duration, the composite solution of lithium nickel cobalt dioxide and tungsten is obtained；
Rate is added by setting, to the precipitant solution is added in the composite solution of the lithium nickel cobalt dioxide and tungsten, to the nickel
The composite solution of cobalt acid lithium and tungsten carries out precipitation process, obtains the solid composite of lithium nickel cobalt dioxide and tungsten；
Step 3, by the solid composite and lithium source of the lithium nickel cobalt dioxide and tungsten, the processing for being roasted and being ground is obtained with core
Shell structure presence and surface layer are coated with the lithium nickel cobalt dioxide composite positive pole of Tungstenic compound layer.
6. according to the method described in claim 5, it is characterized in that, wherein,
In step 1,
Prepare Tungstenic compound solution, comprising: Tungstenic compound is dissolved in water, Tungstenic compound solution needed for being made；It is described to contain
The molar concentration of tungsten compound solution is 0.05~2.5mol/L；And/or
Prepare precipitant solution, comprising: precipitating reagent is dissolved in water, precipitant solution needed for being made；The precipitant solution is rubbed
Your concentration is 0.05~2.5mol/L；
And/or
In step 2,
The lithium nickel cobalt dioxide presoma, comprising: LiNixCoyO2；Wherein, 0.3≤x≤0.9,0.05≤y≤0.4；
And/or
The setting mixing speed, comprising: 100~500rpm；And/or
The first setting duration, comprising: 3-6h；And/or
Rate is added in the setting, comprising: 25~30mL/min；
And/or
In step 3,
The molar ratio of the solid composite of the lithium nickel cobalt dioxide and tungsten and the lithium source is 0.8~1.2:0.8~1.2；And/or
In the lithium nickel cobalt dioxide composite positive pole, the Tungstenic compound, account for the mass fraction of the lithium nickel cobalt dioxide 1~
5%；And/or
The lithium source, comprising: one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate.
7. according to the method described in claim 6, it is characterized in that, wherein,
In step 1,
The Tungstenic compound, comprising: ammonium tungstate or ammonium metatungstate；And/or
The precipitating reagent, comprising: the mixed solution or ammonium hydroxide of ammonium hydroxide and sodium hydroxide and the mixed solution of sodium carbonate；Wherein,
In the mixed solution of the ammonium hydroxide and sodium hydroxide, the molar ratio of ammonium hydroxide and sodium hydroxide is 1~20:25~100；
And/or
In the mixed solution of the ammonium hydroxide and sodium carbonate, the molar ratio of ammonium hydroxide and sodium carbonate is 1~20:25~100；
And/or
In step 2,
X takes 0.6 or 0.8, and/or, y takes 0.2 or 0.4；
And/or
In step 3,
The roasting, comprising: in oxygen atmosphere furnace, after roasting 2~15h with 200~1000 DEG C of temperature condition；And/or
The grinding, comprising: 50~70min of mixed grinding in grinder.
8. the method according to one of claim 5-7, which is characterized in that wherein,
In step 2, precipitation process is carried out to the composite solution of the lithium nickel cobalt dioxide and tungsten, comprising:
After the tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten is deposited to lithium nickel cobalt dioxide surface, it is filtered, receives
Collect solid content, washing and drying process；
And/or
In step 3, the processing for being roasted and being ground, comprising:
First roast the processing ground afterwards, or the processing of first baking after grinding.
9. according to the method described in claim 8, it is characterized in that, wherein,
In step 2, precipitation process is carried out to the composite solution of the lithium nickel cobalt dioxide and tungsten, further includes:
After the tungsten ion by the composite solution of the lithium nickel cobalt dioxide and tungsten is deposited to lithium nickel cobalt dioxide surface, or carry out
It is mixed after the tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten to be deposited to lithium nickel cobalt dioxide surface before the filtering
Object is closed, the second setting duration is stood；
And/or
In step 3, the processing for being roasted and being ground, further includes:
After the roasting, the processing that is also cooled to room temperature；And/or
After the grinding, the processing that is also crushed and be sieved.
10. according to the method described in claim 9, it is characterized in that, wherein,
The second setting duration, comprising: 50~70min；
And/or
The washing, comprising: be deposited to lithium nickel cobalt dioxide table to from the tungsten ion in the composite solution of the lithium nickel cobalt dioxide and tungsten
The solid content being collected into mixture behind face, is washed with deionized；And/or
The drying, comprising: drying.
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| CN109755524A (en) * | 2018-12-29 | 2019-05-14 | 桂林电器科学研究院有限公司 | Modified LiNi0.6Co0.2Mn0.2O2The preparation method and product and battery of tertiary cathode material |
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| CN105185954A (en) * | 2015-06-17 | 2015-12-23 | 电子科技大学 | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof |
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