CN106602016A - Preparation method for ammonium fluoride modified nickel-cobalt-aluminum ternary positive electrode material - Google Patents
Preparation method for ammonium fluoride modified nickel-cobalt-aluminum ternary positive electrode material Download PDFInfo
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- CN106602016A CN106602016A CN201611190846.1A CN201611190846A CN106602016A CN 106602016 A CN106602016 A CN 106602016A CN 201611190846 A CN201611190846 A CN 201611190846A CN 106602016 A CN106602016 A CN 106602016A
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Abstract
The invention relates to the field of the battery material science, and particularly discloses a preparation method for an ammonium fluoride modified nickel-cobalt-aluminum ternary positive electrode material. The preparation method comprises the steps of putting ammonium fluoride granules and lithium nickel cobalt aluminate powder into an agate mortar at a normal temperature, and grinding and mixing uniformly; putting the grinded mixture into a muffle furnace, and performing heating, heat preservation and sintering; and after the obtained product is grinded, sieving by a 400-mesh sieve to obtain a final product. The preparation method disclosed by the invention is simple in process, convenient to operate, easy to realize large-scale production, low in energy consumption, and remarkable in energy-saving effect.
Description
（One）Technical field
The present invention relates to battery material scientific domain, the preparation of the modified nickel cobalt aluminium tertiary cathode material of more particularly to a kind of ammonium fluoride
Method.
（Two）Background technology
Lithium ion battery has the advantages such as high, the big, environmental friendliness of energy density of voltage stabilization, capacity, is widely used in electronic
The fields such as car, electric tool, mobile phone, notebook computer.Positive electrode be determine performance of lithium ion battery critical material, high energy
The positive electrode of metric density, long circulation life and high security has become the trend of future development.Nickelic system's layered cathode material
Material Li (NixM1-x)O2With larger specific discharge capacity, good high rate performance and relatively low cost so as to become important
One of lithium ion cell positive.LiNi0.80Co0.15Al0.05O2（Abbreviation NCA）After cobalt ions and aluminium ion co-doped
Layer structure is stabilized, more preferable electrochemistry and thermodynamic stability is shown, specific discharge capacity is up to 200mAh/g.Therefore it is non-
Often it is adapted to and is hopeful to be applied on the electrokinetic cell of high-energy-density, high power density.
NCA materials still suffer from use some problems, because ternary material has some intrinsic disadvantages, such as in height
Circulation under voltage undergoes phase transition and causes cyclical stability bad, and electronic conductivity is low, and lithium nickel mixing causes high rate performance to be deteriorated.Mesh
Front synthesis NCA materials are most commonly used that high temperature solid-state method, in preparation process, in order to compensate high temperature under elemental lithium volatilization damage
Lose, it will usually be added beyond the lithium salts of stoichiometric proportion, but the lithium salts of excess can't completely volatilize in high temperature solid state reaction,
Part lithium salts can be with Li2In material internal and surface in the form of O, easily with air in CO2And H2O reacts generation
Li2CO3And LiOH, this easily causes in coating process slurry into g., jelly-like, it is difficult to complete to be coated with film-making, and the carbon produced after absorbing water
Sour lithium produces carbon dioxide with hydrofluoric acid reaction micro in electrolyte, causes high temperature inflatable and cycle performance to decline.Additionally, high
Ni under de- lithium state4+Strong oxidizing property tend to reduction generate Ni3+And discharge oxygen and cause heat endurance bad, security is poor.
In order to reduce positive electrode residual lithium salt impurity content and reduce its pH value, improve the electrochemistry of positive electrode
Can, people have carried out various researchs.First, in material preparation process, the extra proportion that lithium salts feeds intake is reduced, or extends high temperature
The solid phase reaction time promotes excessive elemental lithium to volatilize more completely, so as to control the content of residual lithium salt impurity；2nd, by positive pole material
Material water, bicarbonate, organic acid or organic solvent carry out cyclic washing or reaction, then at carrying out separation of solid and liquid and being dried
Reason；3rd, carry out cladding on positive electrode surface and form it into one layer of clad, improve the cyclical stability and heating power of high-nickel material
Learn performance.Surface coated material has TiO2、AlF3、Al2O3、SiO2、AlPO4、LiAlO2、LiVO3、LiMn2O4Deng research table
Bright these stable oxide, phosphide or lithium salts can avoid nickelic system's stratified material in high de- lithium state and in electrolyte
The HF of trace reacts to isolate and reduce pH value, improves the cyclical stability of material.
Here emphasis has a talk the cladding of fluoride, and Chinese patent CN103367740A discloses a kind of " calcirm-fluoride cladding
The method of nickel-cobalt lithium manganate cathode material ", the patent has synthesized calcirm-fluoride and has coated nickel-cobalt lithium manganate material by solwution method, first
Using calcium nitrate and ammonium fluoride synthesis calcirm-fluoride, nickel-cobalt lithium manganate cathode material is then added in aqueous, dispersed with stirring is equal
After even, the roasting in Muffle furnace.It is low compared with raw material that whole experiment process takes longer and resulting materials capacity first.In
State's patent CN103022502A is disclosed " the compound coating method of anode material for lithium-ion batteries ", and the patent is closed using solwution method
Into the fluoride of La, Al, Mg, and positive electrode is added thereto, agitation and filtration drying, and roasting.The process energy consumption is larger, system
Standby overlong time, is unfavorable for industrialized production.
（Three）The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of residual alkali on reduction nickel cobalt lithium aluminate ternary material surface
Amount, improves the preparation method of the modified nickel cobalt aluminium tertiary cathode material of ammonium fluoride of long circulating conservation rate.
The present invention is achieved through the following technical solutions：
A kind of preparation method of the modified nickel cobalt aluminium tertiary cathode material of ammonium fluoride, comprises the steps：
（1）Under normal temperature, ammonium fluoride particle and nickel cobalt aluminic acid lithium powder are placed in agate mortar, grinding is well mixed it；
（2）Mixture after grinding is placed in Muffle furnace, is heated up and heat preservation sintering；
（3）After products therefrom is ground, 400 mesh sieves are crossed, obtain final products.
It is contemplated that reducing the residual alkali amount on nickel cobalt lithium aluminate ternary material surface, long circulating conservation rate is improved.And provide
A kind of preparation method of the modified nickel cobalt aluminium positive electrode of ammonium fluoride.The material residual alkali amount and pH value of gained is all low compared with raw material, and
With higher charge/discharge capacity, good high rate performance and higher cyclical stability.
The present invention more excellent technical scheme be：
Step（1）In, ammonium fluoride particle is 0.002-0.01 with the mass ratio of nickel cobalt aluminic acid lithium powder:1, preferred 0.003-
0.008:1, more optimizedly 0.003：1, both mixed grinding 20-60min, preferred 30-50min, more optimizedly 30min.
Step（2）In, Muffle furnace is warming up to 300-500 DEG C, and heat preservation sintering 3-5h with the programming rate of 5 DEG C/min；It is excellent
Choosing is warming up to 500 DEG C, and heat preservation sintering 3h.
The present invention carries out coating modification to nickel cobalt aluminium tertiary cathode material using ammonium fluoride dry grinding, and fluorine is because with highest
Electronegativity and very high free energy, after the perfluorinated process of material, dissolvings of the HF to transition metal can be reduced, suppress cyclic process
The rising of middle electro transfer impedance, and surface texture of the stabilizing material in charge and discharge process is can guarantee that, improve the electrification of material
Learn performance.
When the mass ratio of ammonium fluoride and nickel cobalt lithium aluminate is 0.003：When 1, milling time is 30min, is obtained after grinding
500 DEG C of sintering 3h of product Jing, the final product for obtaining, first week discharge capacity reaches 174.8mAh/g under 0.2C multiplying powers, under 1C multiplying powers
First week discharge capacity is 160.1mAh/g, 11mAh/g higher than raw material or so, and after circulation 110 weeks, capability retention reaches
93.38%, compare raw material and improve 10%；And under 8C circulations, capacity is still up to 125.9mAh/g, improves the circulation of material
Stability and high rate performance.
It is method of the present invention process is simple, easy to operate, it is easy to which that large-scale production, energy consumption is low, and energy-saving effect is notable.
（Four）Description of the drawings
Below in conjunction with the accompanying drawings the present invention is further illustrated.
Fig. 1 is in the embodiment of the present invention 1,5,6, nickel cobalt aluminium tertiary cathode material and compound 0.3%, 0.5%, 0.8% mass
Cycle life figure of the nickel cobalt aluminium tertiary cathode material of ammonium fluoride cladding under 1C multiplying powers；
Fig. 2 is the fluorination of nickel cobalt aluminium tertiary cathode material and compound 0.3%, 0.5%, 0.8% mass in the embodiment of the present invention 1,5,6
High rate performance figure of the nickel cobalt aluminium tertiary cathode material of ammonium cladding under different multiplying；
Fig. 3 is the scanning electron microscope (SEM) photograph of nickel cobalt aluminic acid lithium powder；
Fig. 4 is that in embodiment 1, ammonium fluoride coats the scanning electron microscope (SEM) photograph of nickel cobalt aluminium tertiary cathode material.
（Five）Specific embodiment
With reference to embodiment, the invention will be further described.
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1：
（1）In mass ratio it is 0.003 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.3%-1.
The electrochemistry of constant current charge-discharge test anode material of lithium battery is carried out using Wuhan indigo plant electricity CT2001A discharge and recharges instrument
Energy.Experimental cell is carried out in the glove box full of argon gas, and the electrolyte for using is LiPF6/EC+DMC+EMC（Volume ratio 1：
1：1）, barrier film is the type barrier films of Celgard 2400；It is metal lithium sheet to electrode.The chemical property of material adopts CR2032 type knobs
Button battery is investigated.
PVDF is dissolved in NMP, the PVDF solution that mass fraction is 4% is prepared, stirring is placed in baking oven 80 DEG C and does
It is standby after dry 12h.The product and nickel cobalt manganese raw material used, conductive carbon black Super of gained after coating in embodiment 1 respectively
P, conductive carbon black KS and above-mentioned PVDF solution are according to mass ratio 88:3:3:6 mixing, after being sufficiently stirred for, slurries are uniformly coated on
On aluminium foil, rolled with double roller tablet press machine after 120 DEG C of vacuum drying 12h.The electrode slice of a diameter of 10mm is made with sheet-punching machine, then
Electrode slice is weighed, 120 DEG C of vacuum drying 5h in being positioned over glove box, are assembled into CR2032 type button cells, by button cell
Place and carry out charge-discharge test after 8h.
Cycle performance curve：At 25 ± 1 DEG C, voltage range is 3.0-4.3V (Vs Li+/ Li) under perseverance is carried out to battery
Stream charge-discharge test and high rate performance test.
Test result shows that first week discharge capacity reaches 174.8mAh/g under 0.2C multiplying powers, first week discharge capacity under 1C multiplying powers
For 160.1mAh/g, after circulating 110 weeks, capability retention compares raw material and improves 10% up to 93.38%.And under 8C circulations,
Capacity is still up to 125.9mAh/g, and this shows that the cycle performance of the sample after ammonium fluoride cladding has and significantly improves, while first
Secondary discharge capacity is not reduced.Additionally, after cladding ammonium fluoride, the pH value and residual alkali amount of material have all dropped than raw material
It is low, therefore improve the processing characteristics of material（Refer to accompanying drawing 1, accompanying drawing 2 and table 1, table 2）.
And as shown in accompanying drawing 3 and accompanying drawing 4, using ESEM as can be seen that prepared nickel cobalt lithium aluminate cathode material
It is made up of fine and close spherical particle, neat in edge, shape is regular, and surface is more smooth.And the nickel after perfluorinated ammonium coating modification
Cobalt lithium aluminate cathode material, its rough surface significantly can find out a thin layer floccule on surface.
Embodiment 2：
（1）In mass ratio it is 0.003 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature：1 is placed in agate mortar, grinds
Mill 20min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.3%-2.
Embodiment 3：
（1）In mass ratio it is 0.003 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 60min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products.It is designated as NCA-F-0.3%-3.
Embodiment 4：
（1）In mass ratio it is 0.002 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.2%-1.
Embodiment 5：
（1）In mass ratio it is 0.005 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products.It is designated as NCA-F-0.5%-1.
Button electrical test results show that first week discharge capacity reaches 176.0mAh/g, head Zhou Fang electricity under 1C multiplying powers under 0.2C multiplying powers
Capacity is 161.1mAh/g, and after circulating 110 weeks, capability retention compares raw material and improve 7% up to 89.20%（Refer to the He of accompanying drawing 1
Table 1）.
Embodiment 6：
（1）In mass ratio it is 0.008 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.8%-1.
Button electrical test results show that first week discharge capacity reaches 172.7mAh/g, head Zhou Fang electricity under 1C multiplying powers under 0.2C multiplying powers
Capacity is 158.2mAh/g, and after circulating 110 weeks, capability retention compares raw material and improve 8% up to 90.27%（Refer to the He of accompanying drawing 1
Table 1）.
Embodiment 7：
（1）In mass ratio it is 0.01 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinding
30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-1.0%-1.
Embodiment 8：
（1）In mass ratio it is 0.003 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 300 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.3%-4.
Embodiment 9：
（1）In mass ratio it is 0.003 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 400 DEG C are warming up to, and be incubated 3h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.3%-5.
Embodiment 10：
（1）In mass ratio it is 0.003 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 4h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.3%-6.
Embodiment 11：
（1）In mass ratio it is 0.003 by ammonium fluoride particle and nickel cobalt aluminic acid lithium powder under normal temperature:1 is placed in agate mortar, grinds
Mill 30min so as to be well mixed；
（2）Mixture after grinding is placed in Muffle furnace, with the programming rate of 5 DEG C/min 500 DEG C are warming up to, and be incubated 5h；
（3）After by the product grinding of gained, 400 mesh sieve, and obtain final products, are designated as NCA-F-0.3%-7.
From above-described embodiment as can be seen that after the perfluorinated process of nickel cobalt lithium aluminate cathode material, not only reducing ternary material
The residual alkali amount and pH value on material surface, and inhibit the rising of electro transfer impedance in cyclic process, the length that improve material to follow
Environmentally friendly holdup, improves its chemical property.
Although above in conjunction with figure, invention has been described, the invention is not limited in above-mentioned specific embodiment party
Formula, above-mentioned specific embodiment is only schematic, rather than restricted, and one of ordinary skill in the art is at this
Under bright enlightenment, without deviating from the spirit of the invention, above-mentioned embodiment can also be changed and changed, these
Belong within the protection of the present invention.
Claims (6)
1. the preparation method of the modified nickel cobalt aluminium tertiary cathode material of a kind of ammonium fluoride, it is characterized by, comprise the steps：（1）Often
Under temperature, ammonium fluoride particle and nickel cobalt aluminic acid lithium powder are placed in agate mortar, grinding is well mixed it；（2）After grinding
Mixture be placed in Muffle furnace, heat up and heat preservation sintering；（3）After products therefrom is ground, 400 mesh sieves are crossed, finally produced
Product.
2. the preparation method of the modified nickel cobalt aluminium tertiary cathode material of ammonium fluoride according to claim 1, it is characterised in that：Step
Suddenly（1）In, ammonium fluoride particle is 0.002-0.01 with the mass ratio of nickel cobalt aluminic acid lithium powder:1, both mixed grinding 20-
60min。
3. the preparation method of the modified nickel cobalt aluminium tertiary cathode material of ammonium fluoride according to claim 1, it is characterised in that：Step
Suddenly（2）In, Muffle furnace is warming up to 300-500 DEG C, and heat preservation sintering 3-5h with the programming rate of 5 DEG C/min.
4. the preparation method of the modified nickel cobalt aluminium tertiary cathode material of ammonium fluoride according to claim 1 and 2, its feature exists
In：Step（1）In, in, ammonium fluoride particle is 0.003-0.008 with the mass ratio of nickel cobalt aluminic acid lithium powder:1, both grind in mixing
Mill 30-50min.
5. the preparation method of the modified nickel cobalt aluminium tertiary cathode material of ammonium fluoride according to claim 1 and 2, its feature exists
In：Step（1）In, in, ammonium fluoride particle is 0.003 with the mass ratio of nickel cobalt aluminic acid lithium powder：1, both mixed grindings
30min。
6. the preparation method of the modified nickel cobalt aluminium tertiary cathode material of ammonium fluoride according to claim 1 or 3, its feature exists
In：Step（2）In, Muffle furnace is warming up to 500 DEG C, and heat preservation sintering 3h with the programming rate of 5 DEG C/min.
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Cited By (12)
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| CN108232131A (en) * | 2017-12-06 | 2018-06-29 | 欣旺达电子股份有限公司 | Metal fluoride cladding ternary material and preparation method thereof |
| CN108598380A (en) * | 2018-03-02 | 2018-09-28 | 圣戈莱（北京）科技有限公司 | A kind of preparation method of surface fluorination and modification tertiary cathode material |
| CN108832104A (en) * | 2018-06-20 | 2018-11-16 | 合肥乘电科技有限责任公司 | A kind of preparation method of aluminum fluoride cladding nickel cobalt aluminic acid lithium material |
| CN108963212A (en) * | 2018-06-28 | 2018-12-07 | 内蒙古华夏新材料科技有限公司 | A kind of anode material for lithium ion battery surface fluorination and modification process |
| CN109286006A (en) * | 2018-09-18 | 2019-01-29 | 华北电力大学 | A kind of preparation method being fluorinated carbon coating nickel-cobalt-manganternary ternary anode material |
| CN109326783A (en) * | 2018-10-12 | 2019-02-12 | 合肥国轩高科动力能源有限公司 | Modified NCM ternary cathode material and preparation method thereof |
| CN110931735A (en) * | 2019-11-15 | 2020-03-27 | 中国科学院宁波材料技术与工程研究所 | Modified composite material, preparation method thereof, and positive electrode material and lithium battery comprising modified composite material |
| CN111009645A (en) * | 2019-11-27 | 2020-04-14 | 宜宾锂宝新材料有限公司 | graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material |
| CN112194195A (en) * | 2020-08-27 | 2021-01-08 | 浙江美都海创锂电科技有限公司 | Preparation method of NCA (negative polarity anodic oxidation) cathode material doped, coated and modified by one-step method |
| CN114665097A (en) * | 2022-04-20 | 2022-06-24 | 蜂巢能源科技股份有限公司 | Cobalt-free positive electrode material and preparation method and application thereof |
| CN115028211A (en) * | 2022-06-10 | 2022-09-09 | 天津巴莫科技有限责任公司 | Fluorine-doped nickel-cobalt-manganese-lithium ternary material and preparation method thereof |
| CN115745021A (en) * | 2022-11-15 | 2023-03-07 | 乳源东阳光新能源材料有限公司 | Method for removing residual lithium in high-nickel ternary cathode material |
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| CN111009645A (en) * | 2019-11-27 | 2020-04-14 | 宜宾锂宝新材料有限公司 | graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material |
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| CN114665097A (en) * | 2022-04-20 | 2022-06-24 | 蜂巢能源科技股份有限公司 | Cobalt-free positive electrode material and preparation method and application thereof |
| CN115028211A (en) * | 2022-06-10 | 2022-09-09 | 天津巴莫科技有限责任公司 | Fluorine-doped nickel-cobalt-manganese-lithium ternary material and preparation method thereof |
| CN115745021A (en) * | 2022-11-15 | 2023-03-07 | 乳源东阳光新能源材料有限公司 | Method for removing residual lithium in high-nickel ternary cathode material |
| CN115745021B (en) * | 2022-11-15 | 2024-05-31 | 乳源东阳光新能源材料有限公司 | Method for removing residual lithium in high-nickel ternary cathode material |
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