CN110400921A - A kind of preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material - Google Patents
A kind of preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material Download PDFInfo
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- CN110400921A CN110400921A CN201910647493.0A CN201910647493A CN110400921A CN 110400921 A CN110400921 A CN 110400921A CN 201910647493 A CN201910647493 A CN 201910647493A CN 110400921 A CN110400921 A CN 110400921A
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Abstract
The present invention relates to a kind of preparation methods of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material, it includes that acetone is added into the mixture of lithia, lithium fluoride, vanadium trioxide and antimony oxide in (1), it is dried after ball milling, first time calcining is carried out, cooling, grinding obtains Sb doped fluorine vanadyl lithium powder；(2) ball milling after mixing Sb doped fluorine vanadyl lithium powder, glucose and ethyl alcohol is evaporated ethyl alcohol, carries out second and calcines, and obtains carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material.This method simple process, operation is easy, energy consumption is lower, raw material are cheap and easily-available, and it is superior to prepare resulting positive electrode chemical property.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of carbon-coated antimony doping rock salt structure
The preparation method of fluorine vanadyl lithium anode material.
Background technique
Lithium ion battery has the excellent chemical properties such as high voltage, high-energy density, is widely used in 3C, electronic vapour
The development of vehicle and energy storage field, especially electric car is even more the further expansion demand of lithium ion battery, also to its energy
More stringent requirements are proposed for density.In order to develop advanced lithium ion battery, people carry out the positive electrode of high-energy density
A large amount of research, current research, which is concentrated mainly on, improves polyanionic compound, spinelle and layered oxide, from structure
On say, the unexpected cation disorder of these positive electrodes and phase transformation would generally reduce electrode performance.2014, america's MIT
The unordered rock salt positive electrode Li of rich lithium is studying in Ceder seminar1.211Mo0.467Cr0.3O2When, it is found that its specific discharge capacity is up to
280mAh/g, the research cause rapidly the interest of people, thus the research of the rich unordered rock salt material of lithium is spread out.
In recent years, for rock salt structure fluorine vanadyl lithium (Li2VO2F research extreme heat), such as Chinese patent application
201710868151.2, which disclose it, can be used as additive and carries out benefit lithium to lithium ion cell positive, obtain a kind of high capacity
Lithium ion battery.But go deep into research, people gradually have found fluorine vanadyl lithium, and as positive electrode, there are following
Problem: (1) material surface oxygen can be deviate under high voltage, can react to form SEI film with electrolyte after aoxidizing, cause for the first time
The irreversible capacity that discharges increases；(2) ionic conductivity is poor, causes high rate performance poor；(3) voltage platform declines in cyclic process
Drop.In order to solve these problems, people begin trying to be modified the rock salt material.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, a kind of carbon-coated antimony doping rock salt structure is provided
The preparation method of fluorine vanadyl lithium anode material, this method can effectively improve ionic conductivity of the fluorine vanadyl lithium as positive electrode
And cycle performance.
The preparation method of carbon-coated antimony of the present invention doping rock salt structure fluorine vanadyl lithium anode material the following steps are included:
(1) acetone is added into the mixture of lithia, lithium fluoride, vanadium trioxide and antimony oxide, is dried after ball milling
It is dry, first time calcining is carried out, cooling, grinding obtains Sb doped fluorine vanadyl lithium powder；
(2) ball milling after mixing Sb doped fluorine vanadyl lithium powder, glucose and ethyl alcohol, is evaporated ethyl alcohol, is forged for the second time
It burns, obtains carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material；
Wherein, the molar ratio of the lithia, lithium fluoride, vanadium trioxide and antimony oxide is 2.2:2:1-x:x,
The mass ratio of 0.01≤x≤0.05, the Sb doped fluorine vanadyl lithium powder and glucose is 6:1~8:1.
Further, the molar ratio of the lithia, lithium fluoride, vanadium trioxide and antimony oxide is 2.2:2:
The mass ratio of 0.97:0.03, the Sb doped fluorine vanadyl lithium powder and glucose is 7:1.
Further, the first time calcining carries out in oxygen atmosphere at 800 DEG C~1000 DEG C, calcination time 8h
~12h.
Further, second of calcining carries out in nitrogen atmosphere at 500 DEG C~550 DEG C, calcination time 4h
~6h.
Further, the first time calcining carries out in oxygen atmosphere at 900 DEG C, calcination time 10h；Described
Secondary clacining carries out in nitrogen atmosphere at 530 DEG C, calcination time 5h.
Another aspect of the present invention, which is additionally provided, adulterates rock salt structure fluorine vanadyl by the carbon-coated antimony that preceding method is prepared
Lithium anode material.
Beneficial effects of the present invention:
The invention discloses a kind of preparation methods of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material, in fluorine oxygen
High-valence state antimony ion Sb is adulterated in vanadium lithium basic material5+Li-Sb is formed, the transport of lithium ion can be promoted, overcome ionic conduction
The poor problem of property.After the present invention carries out Sb doped and charcoal cladding to fluorine vanadyl lithium, preferable chemical property is shown, when 1C
First discharge specific capacity is 300mAh/g~320mAh/g, and capacity keeps stablizing in cyclic process.
Detailed description of the invention
Fig. 1 is the capacity comparison that carbon-coated antimony adulterates that fluorine vanadyl lithium anode material prepares battery under the conditions of 1C and 40 DEG C
Figure；
Fig. 2 is the coulombic efficiency figure that carbon-coated antimony adulterates fluorine vanadyl lithium anode material.
Specific embodiment
The performance that the invention will now be described in detail with reference to the accompanying drawings, but they and do not constitute a limitation of the invention, only
It is for example.Keep advantages of the present invention more clear by explanation simultaneously and is readily appreciated that.
The preparation of 1 fluorine vanadyl lithium anode material (Z0) of embodiment
By 32.87g lithia (excessive 10%, compensate lithium source under high temperature and lose), tri- oxygen of 25.94g lithium fluoride and 74.94g
Change two vanadium to be put into ball grinder, molar ratio Li:V:F=2:1:1, is added after a small amount of acetone at 300 rpm that ball milling is for 24 hours.It obtains
Mixture is dried in air dry oven, is put into oxygen atmosphere tube furnace and is calcined, and calcination temperature is 900 DEG C, and calcination time is
10h, after naturally cooling to room temperature, grinding obtains Li2VO2F(K)。
The preparation of 2 Sb doped fluorine vanadyl lithium anode material (Z1) of embodiment
32.87g lithia (excessive 10%, compensate lithium source under high temperature and lose), 25.94g lithium fluoride, 72.69g tri- are aoxidized
Two vanadium and 4.37g antimony oxide are put into ball grinder, and a small amount of acetone is added in molar ratio Li:V:Sb:F=2:0.97:0.03:1
Ball milling is for 24 hours at 300 rpm afterwards.Obtained mixture is dried in air dry oven, is put into oxygen atmosphere tube furnace and is calcined,
Calcination temperature is 900 DEG C, calcination time 10h, after naturally cooling to room temperature, and grinding obtains Sb doped fluorine vanadyl lithium anode material
Expect (Z1).
The preparation of 3 carbon coating fluorine vanadyl lithium anode material (Z2) of embodiment
By 32.87g lithia (excessive 10%, compensate lithium source under high temperature and lose), tri- oxygen of 25.94g lithium fluoride and 74.94g
Change two vanadium to be put into ball grinder, molar ratio Li:V:F=2:1:1, is added after a small amount of acetone at 300 rpm that ball milling is for 24 hours.It obtains
Mixture is dried in air dry oven, is put into progress first time calcination in oxygen atmosphere tube furnace, and calcination temperature is 900 DEG C,
Calcination time is 10h, and after naturally cooling to room temperature, grinding obtains Li2VO2F powder.By 14g Li2VO2F powder, 2g grape
Sugar and ethyl alcohol mixing and ball milling 4h after ethanol evaporation, carry out second in nitrogen atmosphere tube furnace and calcine, calcination temperature 530
DEG C, calcination time 5h obtains carbon coating fluorine vanadyl lithium anode material (Z2).
4 carbon-coated antimony of embodiment adulterates the preparation of fluorine vanadyl lithium anode material (A~T)
Lithia, lithium fluoride, vanadium trioxide and antimony oxide are put into ball grinder, are added after a small amount of acetone
Ball milling is for 24 hours under 300rpm.Obtained mixture is dried in air dry oven, is put into oxygen atmosphere tube furnace and carries out first
Secondary calcination, calcination temperature are 900 DEG C, calcination time 10h, after naturally cooling to room temperature, and grinding obtains Sb doped fluorine vanadyl
Lithium powder.By Sb doped fluorine vanadyl lithium powder, glucose and ethyl alcohol mixing and ball milling 4h, after ethanol evaporation, in nitrogen atmosphere tubular type
It carries out calcining for second in furnace, calcination temperature is 530 DEG C, calcination time 5h, obtains carbon-coated antimony doping fluorine vanadyl lithium anode
Material.Lithia, lithium fluoride, vanadium trioxide and antimony oxide molar ratio M (Li2O): M (LiF): M (V2O3): M
(Sb2O3), the calcination temperature T1 of calcining for the first time, for the first time the calcination time t1 of calcining, Sb doped fluorine vanadyl lithium powder and grape
Mass ratio m (powder): m (glucose) of sugar, the calcination temperature T2 of second of calcining, the calcination time t2 difference of second of calcining
It is as shown in table 1:
Table 1: carbon-coated antimony adulterates the preparation condition of fluorine vanadyl lithium anode material (A~T)
Electrochemical property test
By the different sample assemblies of Examples 1 to 4 preparation at CR2032 type button cell, in 2.5V~4.5V voltage range
It is interior, charge and discharge are carried out under 25 DEG C, 1C multiplying power, gained test result is as shown in table 1:
From table 1 it follows that the molar ratio of holding vanadium trioxide and antimony oxide is when carrying out Sb doped
0.01~0.05, it is 6:1~8:1 that the mass ratio of Sb doped fluorine vanadyl lithium powder and glucose is kept when carrying out carbon coating, can
Discharge capacity is 260.7mAh/g~273.4mAh/g's after to obtain capacity retention ratio be 84.2%~86.7%, circulation 50 is enclosed
Positive electrode meets production and living needs.And the other materials in table 1, especially other carbon-coated antimonies doping fluorine vanadyl lithium are just
Pole material, although can also be improved discharge capacity after 50 circle of capacity retention ratio and circulation, incremental amplitude is little, hence it is evident that is lower than
Aforementioned positive electrode material.
The capacity that the preferable positive electrode of aforementioned test performance is prepared to battery under the conditions of 1C and 40 DEG C compares, as a result such as
Shown in Fig. 1.It will be seen from figure 1 that the capacity retention ratio of B, C, D, G, H, I, L, M and N are respectively 84.1%, 88.4%,
86.5%, 87.2%, 89.1%, 86.9%, 87.3%, 87.7% and 88.0%, capacity retention ratio when higher than 25 DEG C, thus it is speculated that
Further reduction process has occurred for the vanadium in positive electrode.
Similarly, the preferable positive electrode of aforementioned test performance is carried out to coulomb effect under room temperature, 0.1C current density
Rate testing experiment, as a result as shown in Figure 2.Figure it is seen that the coulombic efficiency of B, C, D, G, H, I, L, M and N be 92.2%,
92.5%, 93.1%, 92.9%, 93.6%, 93.4%, 92.8%, 92.7% and 93.3%.Be speculated as Li-Sb promote lithium from
The transport of son, and the presence of carbon can further enhance the charge transmission on combination electrode surface, and improve coulombic efficiency for the first time.
The content that this specification is not described in detail belongs to the prior art well known to professional and technical personnel in the field.
Claims (6)
1. a kind of preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material, it is characterised in that: including following
Step:
(1) acetone is added into the mixture of lithia, lithium fluoride, vanadium trioxide and antimony oxide, is dried after ball milling, into
Row is calcined for the first time, and cooling, grinding obtains Sb doped fluorine vanadyl lithium powder；
(2) ball milling after mixing Sb doped fluorine vanadyl lithium powder, glucose and ethyl alcohol is evaporated ethyl alcohol, carries out second and calcines, obtains
Rock salt structure fluorine vanadyl lithium anode material is adulterated to carbon-coated antimony；
Wherein, the molar ratio of the lithia, lithium fluoride, vanadium trioxide and antimony oxide be 2.2:2:1-x:x, 0.01≤
The mass ratio of x≤0.05, the Sb doped fluorine vanadyl lithium powder and glucose is 6:1~8:1.
2. the preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material according to claim 1, special
Sign is: the lithia, lithium fluoride, vanadium trioxide and antimony oxide molar ratio be 2.2:2:0.97:0.03, it is described
The mass ratio of Sb doped fluorine vanadyl lithium powder and glucose is 7:1.
3. the preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material according to claim 1, special
Sign is: the first time calcining carries out in oxygen atmosphere at 800 DEG C~1000 DEG C, and calcination time is 8h~12h.
4. the preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material according to claim 3, special
Sign is: second of calcining carries out in nitrogen atmosphere at 500 DEG C~550 DEG C, and calcination time is 4h~6h.
5. the preparation method of carbon-coated antimony doping rock salt structure fluorine vanadyl lithium anode material according to claim 4, special
Sign is: the first time calcining carries out in oxygen atmosphere at 900 DEG C, calcination time 10h；Second of calcining exists
It is carried out in nitrogen atmosphere at 530 DEG C, calcination time 5h.
6. a kind of carbon-coated antimony adulterates rock salt structure fluorine vanadyl lithium anode material, by according to any one of claims 1 to 5
Preparation method obtains.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112725843A (en) * | 2020-12-25 | 2021-04-30 | 武汉大学 | Molten salt electrochemical preparation method of carbon-coated low-melting-point metal nano material |
| CN113314701A (en) * | 2021-05-21 | 2021-08-27 | 上海大学 | Carbon-coated cation disordered positive electrode material, preparation method and lithium ion battery |
| WO2024046228A1 (en) * | 2022-08-31 | 2024-03-07 | 天津巴莫科技有限责任公司 | High-entropy positive electrode material, and preparation method therefor and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112725843A (en) * | 2020-12-25 | 2021-04-30 | 武汉大学 | Molten salt electrochemical preparation method of carbon-coated low-melting-point metal nano material |
| CN112725843B (en) * | 2020-12-25 | 2022-06-03 | 武汉大学 | Molten salt electrochemical preparation method of carbon-coated low-melting-point metal nano material |
| CN113314701A (en) * | 2021-05-21 | 2021-08-27 | 上海大学 | Carbon-coated cation disordered positive electrode material, preparation method and lithium ion battery |
| WO2024046228A1 (en) * | 2022-08-31 | 2024-03-07 | 天津巴莫科技有限责任公司 | High-entropy positive electrode material, and preparation method therefor and use thereof |
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