CN110112383A - The nickelic tertiary cathode material and preparation method thereof of titanium phosphate aluminium lithium cladding - Google Patents
The nickelic tertiary cathode material and preparation method thereof of titanium phosphate aluminium lithium cladding Download PDFInfo
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- CN110112383A CN110112383A CN201910308153.5A CN201910308153A CN110112383A CN 110112383 A CN110112383 A CN 110112383A CN 201910308153 A CN201910308153 A CN 201910308153A CN 110112383 A CN110112383 A CN 110112383A
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention relates to the nickelic tertiary cathode materials and preparation method thereof that field of lithium ion battery anode more particularly to a kind of titanium phosphate aluminium lithium coat.The preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding, comprising steps of 1) preparing titanium phosphate aluminium lithium covering liquid: by LiNO3、Al(NO3)3·9H2O, butyl titanate and tributyl phosphate are uniformly mixed in ethanol, are slow added into ethylenediamine tetra-acetic acid and citric acid, are uniformly mixing to obtain titanium phosphate aluminium lithium covering liquid；2) it coats: nickelic tertiary cathode material is added in titanium phosphate aluminium lithium covering liquid, successively obtain the nickelic tertiary cathode material of titanium phosphate aluminium cladding after drying, calcination process after mixing evenly.The present invention is coated using the titanium phosphate aluminium lithium material of high structural stability, since the high structural stability of titanium phosphate aluminium lithium is conducive to inhibit high-nickel material side reaction, to inhibit the appearance of micro-crack, to inhibit the decaying of capacity, improves capacity retention ratio.
Description
Technical field
The present invention relates to the nickelic ternarys that field of lithium ion battery anode more particularly to a kind of titanium phosphate aluminium lithium coat
Positive electrode and preparation method thereof.
Background technique
In recent years, the nickelic tertiary cathode material (NCM) of ternary material Cao was due to energy density height, good cycle, peace
The advantages that performance is high entirely has been considered as one of most promising positive electrode.
But the capacity of nickelic NCM material is easy rapid decay, is mainly due to unstable Ni4+Presence.In NCM
In positive electrode charging process, anisotropic volume change can occur for micro-crack, this can damage the mechanical stability of anode, and
Chemical degradation caused by aggravation is corroded due to electrolyte；In addition, the Ni in transition metal layer2+It occupies lithium vacancy and forms cationic mix
Row.With the increase of Ni content, the average valence of Ni is gradually increased, and the interlamellar spacing of ternary material is caused to be gradually reduced.Ni, Mn and
Co is no longer uniformly distributed in transition metal layer, but Cluster Phenomenon occurs.Therefore structural stability, the heat of NCM high-nickel material
Stability is not so good as low nickel material.
Currently, people are mainly the performance for improving ternary high-nickel material by surface coated means, wherein common
Covering material has metal oxide, fluoride, phosphate etc., but the cycle performance of battery cannot effectively be changed after coating
It is kind.
Summary of the invention
In order to solve problem above, the object of the present invention is to provide a kind of nickelic tertiary cathode materials of titanium phosphate aluminium lithium cladding
Material and preparation method thereof, can significantly improve the cycle performance of nickelic tertiary cathode material.
To achieve the above object, the preparation side of the nickelic tertiary cathode material of the titanium phosphate aluminium cladding designed by the present invention
Method, comprising steps of
1) titanium phosphate aluminium lithium covering liquid is prepared: by LiNO3、Al(NO3)3·9H2O, butyl titanate and tributyl phosphate exist
It is uniformly mixed in ethyl alcohol, is slow added into ethylenediamine tetra-acetic acid and citric acid, is uniformly mixing to obtain titanium phosphate aluminium lithium covering liquid；
2) it coats: nickelic tertiary cathode material being added in titanium phosphate aluminium lithium covering liquid, is successively passed through after mixing evenly
The nickelic tertiary cathode material of titanium phosphate aluminium cladding is obtained after drying, calcination process.
Compared with existing metal oxide, fluoride, Phosphate coating material, the present invention is using high structural stability
Titanium phosphate aluminium lithium material is coated, since the high structural stability of titanium phosphate aluminium lithium is conducive to inhibit high-nickel material side reaction,
To inhibit the appearance of micro-crack, to inhibit the decaying of capacity, capacity retention ratio is improved.
Preferably, in the step 1), Li in molar ratio+:Al3+:Ti4+:PO4 3-=1.3:0.3:1.7:3 is added
LiNO3、Al(NO3)3·9H2O, butyl titanate and tributyl phosphate, and Li in molar ratio++Al3+: ethylenediamine tetra-acetic acid: lemon
Lemon acid=1:1:1.4~1.6, obtained titanium phosphate aluminium lithium covering liquid are Li1.3Al0.3Ti1.7(PO4)3Covering liquid.Ethylenediamine tetrem
Acid and citric acid are complexed metal ion as complexing agent, and in addition citric acid can also be adjusted the pH of reaction solution
Prevent the hydrolysis of butyl titanate too fast to control the hydrolysis rate of butyl titanate, tetrabutyl titanate hydrolysis product is titanium dioxide
Titanium.
Preferably, in the step 2), Li is controlled1.3Al0.3Ti1.7(PO4)3Li in covering liquid1.3Al0.3Ti1.7
(PO4)3Quality account for nickelic tertiary cathode material and Li1.3Al0.3Ti1.7(PO4)3The 1~3% of covering liquid gross mass.Covering amount
It will affect the performance of the nickelic tertiary cathode material of titanium phosphate aluminium cladding too much.
Preferably, calcination process in the step 2) are as follows: heat 3~7h at 450~650 DEG C in tube furnace.
Preferably, in the step 2), the preparation process of nickelic tertiary cathode material are as follows: in N2It, will under atmosphere
NiSO4·6H2O solution, CoSO4·7H2O solution, MnSO4·H2O solution, NaOH solution, NH3·H2O solution is uniformly mixed and obtains
[Ni0.90Co0.05Mn0.05](OH)2Presoma controls molar ratio Ni:Co:Mn=90:5:5, controls pH 11.5~12.0；Hydrogen
The molar ratio of sodium oxide molybdena and transition metal is 2:1, and the molar ratio of ammonium hydroxide and transition metal is 1:1；By [Ni0.90Co0.05Mn0.05]
(OH)2After presoma is dry with LiOHH2O mixing, the molar ratio of lithium and transition metal are 1.01~1.03:1, and 700~
O at 800 DEG C28~12h is calcined in atmosphere obtains Li [Ni0.90Co0.05Mn0.05]O2Nickelic tertiary cathode material.
Realizing the preferable technical solution of the present invention is: the preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding,
Comprising steps of
1) titanium phosphate aluminium lithium covering liquid: Li in molar ratio is prepared+:Al3+:Ti4+:PO4 3-=1.3:0.3:1.7:3 is weighed
LiNO3、Al(NO3)3·9H2O, it butyl titanate and tributyl phosphate and is mixed in ethyl alcohol and obtains the first mixed solution, then
Li in molar ratio++Al3+: ethylenediamine tetra-acetic acid: citric acid=1:1:1.5 weighs ethylenediamine tetra-acetic acid and citric acid, and it is mixed in
The second mixed solution is obtained in ethyl alcohol, and the second mixed solution is poured into the first mixed solution and is uniformly mixing to obtain
Li1.3Al0.3Ti1.7(PO4)3Covering liquid；
2) it coats: nickelic tertiary cathode material is added to Li1.3Al0.3Ti1.7(PO4)3It stirs evenly, and controls in covering liquid
Li processed1.3Al0.3Ti1.7(PO4)3Quality account for nickelic tertiary cathode material and Li1.3Al0.3Ti1.7(PO4)3Covering liquid gross mass
2wt% heats 3~7h after drying in tube furnace 450~650 DEG C, obtains the nickelic ternary of titanium phosphate aluminium cladding
Positive electrode.
Detailed description of the invention
The nickelic tertiary cathode material and comparative example for the titanium phosphate aluminium lithium cladding that Fig. 1 obtains for embodiment 2 obtain nickelic
Tertiary cathode material recycles the cycle performance figure of 50 circles under room temperature 1C multiplying power；Wherein 〇 indicates that 50 circle circulations of comparative example are bent
Line, ■ indicate 50 circle cyclic curves of the nickelic tertiary cathode material for the titanium phosphate aluminium lithium cladding that embodiment 2 obtains.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.
To solve the problems, such as existing ternary high-nickel material there are poor circulation, the present invention provides a kind of titanium phosphate aluminium lithium packet
Nickelic tertiary cathode material covered and preparation method thereof, specifically, being silicon source using lithium nitrate as lithium source, aluminum nitrate, metatitanic acid four
Butyl ester is titanium source and tributyl phosphate is phosphorus source, prepares Li1.3Al0.3Ti1.7(PO4)3Covering liquid, then by high-nickel material Li
[Ni0.90Co0.05Mn0.05]O2Immerse Li1.3Al0.3Ti1.7(PO4)3Titanium phosphate aluminium is obtained in covering liquid after drying, heating process
The nickelic tertiary cathode material of lithium cladding.The height that titanium phosphate aluminium lithium of the invention will be coated by specific embodiment below
The preferred embodiment of nickel tertiary cathode material is described in detail.
Embodiment 1
The preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding, comprising steps of
(1) Li is prepared1.3Al0.3Ti1.7(PO4)3Covering liquid: 0.013mol LiNO is weighed by molal quantity3、0.003mol Al
(NO3)3·9H2O, 0.017mol butyl titanate and 0.03mol tributyl phosphate；By above-mentioned LiNO3、Al(NO3)3·
9H2O, butyl titanate and tributyl phosphate are added in 30mL ethyl alcohol and are uniformly mixed, and heat 80 DEG C of stirring 30min and obtain first
Mixed solution；0.016mol ethylenediamine tetra-acetic acid and 0.0224mol citric acid are weighed by molal quantity, by ethylenediamine tetra-acetic acid and lemon
Lemon acid, which is added to be uniformly mixed in 10ml ethyl alcohol, obtains the second mixed solution；Second mixed solution is poured into the first mixed solution
It is uniformly mixing to obtain 52.6gLi1.3Al0.3Ti1.7(PO4)3Covering liquid, wherein Li1.3Al0.3Ti1.7(PO4)3Molal quantity be
0.01mol, quality 3.928g.
(2) Li [Ni is prepared0.90Co0.05Mn0.05]O2High-nickel material: 1.8mol/L NiSO is prepared by molal quantity4·6H2O is molten
Liquid, 0.1mol/LCoSO4·7H2O solution, 0.1mol/L MnSO4·H2O solution, by NiSO4·6H2O solution, CoSO4·7H2O
Solution and MnSO4·H2O solution is in N2Under atmosphere be added reactor in, while into reactor be added 4mol/L NaOH solution and
The NH of 10mol/L is added3·H2It is 11.5 that O, which controls pH value of solution, and precipitating obtains high-nickel material presoma after mixing, by high-nickel material
Presoma be dried after with 2.04mol/L LiOHH2O mixing, and the O at 750 DEG C210h is calcined in atmosphere obtains 340.2g
Li[Ni0.90Co0.05Mn0.05]O2High-nickel material.
(3) it coats: by Li [Ni0.90Co0.05Mn0.05]O2High-nickel material immerses Li1.3Al0.3Ti1.7(PO4)3In covering liquid,
Li1.3Al0.3Ti1.7(PO4)3Quality account for Li [Ni0.90Co0.05Mn0.05]O2High-nickel material and Li1.3Al0.3Ti1.7(PO4)3Cladding
The 1wt% of liquid gross mass stirs 6h at 80 DEG C and obtains mixed liquor, mixed liquor is then placed 120 DEG C of dryings in constant temperature oven
10h obtains powdered mixture, finally powdered mixture is heated 5h in tube furnace at 550 DEG C and obtains titanium phosphate
The nickelic tertiary cathode material of aluminium cladding.
Embodiment 2
The preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding, comprising steps of
(1) Li is prepared1.3Al0.3Ti1.7(PO4)3Covering liquid: 0.013mol LiNO is weighed by molal quantity3、0.003mol Al
(NO3)3·9H2O, 0.017mol butyl titanate and 0.03mol tributyl phosphate；By above-mentioned LiNO3、Al(NO3)3·
9H2O, butyl titanate and tributyl phosphate are added in 30mL ethyl alcohol and are uniformly mixed, and heat 80 DEG C of stirring 30min and obtain first
Mixed solution；0.016mol ethylenediamine tetra-acetic acid and 0.0224mol citric acid are weighed by molal quantity, by ethylenediamine tetra-acetic acid and lemon
Lemon acid, which is added to be uniformly mixed in 10ml ethyl alcohol, obtains the second mixed solution；Second mixed solution is poured into the first mixed solution
It is uniformly mixing to obtain 53.1g Li1.3Al0.3Ti1.7(PO4)3Covering liquid.
(2) Li [Ni is prepared0.90Co0.05Mn0.05]O2High-nickel material: 1.8mol/L NiSO is prepared by molal quantity4·6H2O is molten
Liquid, 0.1mol/LCoSO4·7H2O solution, 0.1mol/L MnSO4·H2O solution, by NiSO4·6H2O solution, CoSO4·7H2O
Solution and MnSO4·H2O solution is in N2Under atmosphere be added reactor in, while into reactor be added 4mol/L NaOH solution and
The NH of 10mol/L is added3·H2It is 11.8 that O, which controls pH value of solution, and precipitating obtains high-nickel material presoma after mixing, by high-nickel material
Presoma be dried after with 2.02mol/L LiOHH2O mixing, and the O at 750 DEG C210h is calcined in atmosphere to obtain
338.2gLi[Ni0.90Co0.05Mn0.05]O2High-nickel material.
(3) it coats: taking 143.3gLi [Ni0.90Co0.05Mn0.05]O2High-nickel material immerses Li1.3Al0.3Ti1.7(PO4)3Cladding
In liquid, Li is controlled1.3Al0.3Ti1.7(PO4)3Quality account for Li [Ni0.90Co0.05Mn0.05]O2High-nickel material and Li1.3Al0.3Ti1.7
(PO4)3The 2wt% of covering liquid gross mass stirs 6h at 80 DEG C and obtains mixed liquor, then places mixed liquor in constant temperature oven
120 DEG C of dry 10h obtain powdered mixture, and powdered mixture is finally heated 5h at 550 DEG C in tube furnace
Obtain the nickelic tertiary cathode material of titanium phosphate aluminium cladding.
Embodiment 3
The preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding, comprising steps of
(1) Li is prepared1.3Al0.3Ti1.7(PO4)3Covering liquid: 0.013mol LiNO is weighed by molal quantity3、0.003mol Al
(NO3)3·9H2O, 0.017mol butyl titanate and 0.03mol tributyl phosphate；By above-mentioned LiNO3、Al(NO3)3·
9H2O, butyl titanate and tributyl phosphate are added in 30mL ethyl alcohol and are uniformly mixed, and heat 80 DEG C of stirring 30min and obtain first
Mixed solution；0.016mol ethylenediamine tetra-acetic acid and 0.0224mol citric acid are weighed by molal quantity, by ethylenediamine tetra-acetic acid and lemon
Lemon acid, which is added to be uniformly mixed in 10ml ethyl alcohol, obtains the second mixed solution；Second mixed solution is poured into the first mixed solution
It is uniformly mixing to obtain 55.2gLi1.3Al0.3Ti1.7(PO4)3Covering liquid.
(2) Li [Ni is prepared0.90Co0.05Mn0.05]O2High-nickel material: 1.8mol/L NiSO is prepared by molal quantity4·6H2O is molten
Liquid, 0.1mol/LCoSO4·7H2O solution, 0.1mol/L MnSO4·H2O solution, by NiSO4·6H2O solution, CoSO4·7H2O
Solution and MnSO4·H2O solution is in N2Under atmosphere be added reactor in, while into reactor be added 4mol/L NaOH solution and
The NH of 10mol/L is added3·H2It is 12.0 that O, which controls pH value of solution, and precipitating obtains high-nickel material presoma after mixing, by high-nickel material
Presoma be dried after with 2.06mol/L LiOHH2O mixing, and the O at 750 DEG C210h is calcined in atmosphere to obtain
342.1gLi[Ni0.90Co0.05Mn0.05]O2High-nickel material.
(3) it coats: taking 75.7gLi [Ni0.90Co0.05Mn0.05]O2High-nickel material immerses Li1.3Al0.3Ti1.7(PO4)3Cladding
In liquid, Li is controlled1.3Al0.3Ti1.7(PO4)3Quality account for Li [Ni0.90Co0.05Mn0.05]O2High-nickel material and Li1.3Al0.3Ti1.7
(PO4)3The 3wt% of covering liquid gross mass stirs 6h at 80 DEG C and obtains mixed liquor, then places mixed liquor in constant temperature oven
120 DEG C of dry 10h obtain powdered mixture, and powdered mixture is finally heated 5h at 550 DEG C in tube furnace
Obtain the nickelic tertiary cathode material of titanium phosphate aluminium cladding.
Comparative example
Comparative example is Li [Ni0.90Co0.05Mn0.05]O2Li in high-nickel material, preparation method and embodiment 1
[Ni0.90Co0.05Mn0.05]O2High-nickel material preparation method is identical.
The Li that the nickelic tertiary cathode material for the titanium phosphate aluminium cladding that Examples 1 to 3 obtains and comparative example are obtained
[Ni0.90Co0.05Mn0.05]O2High-nickel material carries out the test of 50 circle of circulation under room temperature 1C multiplying power, as a result such as table 1, wherein embodiment
Li [the Ni that the nickelic tertiary cathode material and comparative example of 2 obtained titanium phosphate aluminium claddings obtain0.90Co0.05Mn0.05]O2Nickelic material
The capacity retention ratio comparison diagram that material carries out 50 circle of circulation under room temperature 1C multiplying power is as shown in Figure 1.
Table 1
It will be seen from figure 1 that the capacity retention ratio of the nickelic tertiary cathode material for the titanium phosphate aluminium cladding that embodiment 2 obtains
Higher than comparative example, due to Li1.3Al0.3Ti1.7(PO4)3Be coated be conducive to inhibit high-nickel material side reaction.It can from 1 result of table
To find out, the capacity retention ratio of the nickelic tertiary cathode material for the titanium phosphate aluminium cladding that Examples 1 to 3 obtains is also above comparative example
In the Li [Ni that is not coated0.90Co0.05Mn0.05]O2It is nickelic to prove that titanium phosphate aluminium lithium coats by result above for high-nickel material
Material can inhibit the appearance of micro-crack, to inhibit the decaying of capacity, improve capacity retention ratio.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (5)
1. a kind of preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium lithium cladding, which is characterized in that comprising steps of
1) titanium phosphate aluminium lithium covering liquid is prepared: by LiNO3、Al(NO3)3·9H2O, butyl titanate and tributyl phosphate are in ethyl alcohol
In be uniformly mixed, be slow added into ethylenediamine tetra-acetic acid and citric acid, be uniformly mixing to obtain titanium phosphate aluminium lithium covering liquid；
2) coat: by nickelic tertiary cathode material be added in titanium phosphate aluminium lithium covering liquid after mixing evenly successively by it is dry,
The nickelic tertiary cathode material of titanium phosphate aluminium cladding is obtained after calcination process.
2. the preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding according to claim 1, which is characterized in that
In the step 1), Li in molar ratio+:Al3+:Ti4+:PO4 3-LiNO is added in=1.3:0.3:1.7:33、Al(NO3)3·9H2O、
Butyl titanate and tributyl phosphate, and Li in molar ratio++Al3+: ethylenediamine tetra-acetic acid: citric acid=1:1:1.4~1.6 obtains
The titanium phosphate aluminium lithium covering liquid arrived is Li1.3Al0.3Ti1.7(PO4)3Covering liquid.
3. the preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding according to claim 2, which is characterized in that
In the step 2), Li is controlled1.3Al0.3Ti1.7(PO4)3Li in covering liquid1.3Al0.3Ti1.7(PO4)3Quality account for nickelic ternary
Positive electrode and Li1.3Al0.3Ti1.7(PO4)3The 1~3% of covering liquid gross mass.
4. the preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding according to claim 1, which is characterized in that
Calcination process in the step 2) are as follows: heat 3~7h at 450~650 DEG C in tube furnace.
5. the preparation method of the nickelic tertiary cathode material of titanium phosphate aluminium cladding according to claim 1 or 2, feature exist
In, in the step 2), the preparation process of nickelic tertiary cathode material are as follows: in N2Under atmosphere, by NiSO4·6H2O solution,
CoSO4·7H2O solution, MnSO4·H2O solution, NaOH solution, NH3·H2O solution is uniformly mixed and obtains
[Ni0.90Co0.05Mn0.05](OH)2Presoma controls molar ratio Ni:Co:Mn=90:5:5, controls pH 11.5~12.0；Hydrogen
The molar ratio of sodium oxide molybdena and transition metal is 2:1；By [Ni0.90Co0.05Mn0.05](OH)2After presoma is dry with LiOHH2O is mixed
It closes, the molar ratio of lithium and transition metal is 1.01~1.03:1, and the O at 700~800 DEG C28~12h is calcined in atmosphere to obtain
Li[Ni0.90Co0.05Mn0.05]O2Nickelic tertiary cathode material.
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| CN111952560A (en) * | 2020-07-30 | 2020-11-17 | 中科廊坊过程工程研究院 | Composite cathode material, preparation method thereof and lithium ion battery |
| CN111987311A (en) * | 2020-08-12 | 2020-11-24 | 中南大学 | Titanium indium lithium phosphate modified positive electrode material and preparation method thereof |
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| CN115425214A (en) * | 2022-09-29 | 2022-12-02 | 合肥国轩高科动力能源有限公司 | Coating modified high-nickel ternary cathode material, and preparation method and application thereof |
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