CN107403927A - A kind of preparation method of Mg doped titanic acids lithium titanate cathode material - Google Patents
A kind of preparation method of Mg doped titanic acids lithium titanate cathode material Download PDFInfo
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- CN107403927A CN107403927A CN201710560972.XA CN201710560972A CN107403927A CN 107403927 A CN107403927 A CN 107403927A CN 201710560972 A CN201710560972 A CN 201710560972A CN 107403927 A CN107403927 A CN 107403927A
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- lithium titanate
- doped titanic
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- titanate cathode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of preparation method of Mg doped titanic acids lithium titanate cathode material, there are following steps：According to Li4‑xMgxTi5O12Atomic ratio weighs raw material, lithium source excessive 6% respectively, and is put into together in ball grinder with dispersant, wherein, Mg comes from Mg compounds, x=0.1 0.3；Ball grinder is loaded into ball mill, with 400~600 rotating speed, 1~6h of ball milling；Liquid after ball milling is placed in drying box, 120 DEG C of dry 12h；Dried powder is combined in agate mortar, grinding is uniform, obtains lithium titanate precursor；Lithium titanate precursor is placed in tube furnace, at 600~900 DEG C, under air atmosphere, Mg doped titanic acid lithium titanate cathode materials are obtained after being heat-treated 4~8h.By the present invention, Mg doped titanic acid lithium titanate cathode materials are in 100mAhg‑1When its first discharge specific capacity can reach 193.6mAhg‑1。
Description
Technical field
The present invention relates to the preparation field of negative material, specifically a kind of preparation of Mg doped titanic acids lithium titanate cathode material
Method.
Background technology
At present, lithium ion battery has been widely used in various electric equipments, and commercialized lithium ion battery
Negative material is based on carbon material, but carbon material causes battery short circuit, pacified due to easily producing Li dendrite in discharge process
The inferior positions such as full property difference and cycle performance are low.Therefore searching one kind is safe, cyclicity is good, constitutionally stable negative material.
The Li of spinel-type4Ti5O12As lithium ion battery negative material, because the volume for being less than 0.2% in its charge and discharge process becomes
Change, and structure is almost held constant in the process, is referred to as " zero strain " material.Contrasted with carbon material, good cycle performance
It is its remarkable advantage with stable discharge platform.Therefore, it is considered to be a kind of very promising lithium ion battery negative material.But
The problem of poorly conductive, lithium storage content is low be present in lithium titanate material.Therefore prepared using the solid phase method that method is easy and cost is low
The Li of high lithium storage content4Ti5O12Material is still the difficult point studied at present.
The content of the invention
According to technical problem set forth above, and provide a kind of preparation method of Mg doped titanic acids lithium titanate cathode material.This hair
The technological means of bright use is as follows：
A kind of preparation method of Mg doped titanic acids lithium titanate cathode material, it is characterised in that there are following steps：
S1, according to Li4-xMgxTi5O12Atomic ratio weighs raw material, lithium source excessive 6% respectively, and (dispersant does not have same dispersant
Cross ball milling ball) it is put into together in ball grinder, wherein, Mg comes from Mg compounds, x=0.1-0.3；
S2, ball grinder loaded into ball mill, with 400~600 rotating speed, 1~6h of ball milling；
S3, the liquid after ball milling is placed in drying box, 120 DEG C of dry 12h；Dried powder is combined in into agate mortar
In, grinding is uniform, obtains lithium titanate precursor；
S4, lithium titanate precursor is placed in tube furnace, at 600~900 DEG C, under air atmosphere, be heat-treated after 4~8h
To Mg doped titanic acid lithium titanate cathode materials.
The dispersant is ethanol.
The Mg compounds are Mg (CH3COO)2·4H2O, MgO or Mg (OH)2。
By the present invention, Mg doped titanic acid lithium titanate cathode materials are in 100mAhg-1Its first discharge specific capacity when (i.e. 0.57C)
It can reach 193.6mAhg-1(Mg compounds are Mg (OH)2, x=0.2, rotational speed of ball-mill 400, ball milling 3h, it is heat-treated at 800 DEG C
8h), than undoped with lithium titanate anode material 145.3mAhg-1Initial capacity improve 33.2%, while Mg doped titanic acids
Lithium titanate cathode material is maintained at 190.5mAhg by 100 circulations, capacity-1, capability retention 98.4%.Under 10C multiplying powers still
So there is good voltage platform, specific capacity is maintained at 125.2mAhg-1。
The addition of Mg ions in the present invention, it can effectively suppress the growth of lithium titanate particle；Less size will make crystalline substance
Grain more fully contacts with electrolyte, so as to improve the chemical property of electrode.
The present invention can be widely popularized in fields such as the preparations of negative material for the foregoing reasons.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to do simply to introduce, it should be apparent that, drawings in the following description are this hairs
Some bright embodiments, for those of ordinary skill in the art, without having to pay creative labor, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 be the present invention embodiment in XRD test charts (a is Mg doped titanic acid lithium titanate cathode materials, b undoped with
Lithium titanate anode material).
Fig. 2 is that voltage capacitor is bent under the different multiplying undoped with lithium titanate anode material in embodiment of the invention
Line.
Fig. 3 is that voltage capacitor is bent under the different multiplying of Mg doped titanic acid lithium titanate cathode materials in embodiment of the invention
Line.
Fig. 4 is that (a is Mg doped titanic acid lithium titanate cathode materials to stable circulation linearity curve, and b is not in embodiment of the invention
Doped titanic acid lithium titanate cathode material).
Fig. 5 is that (a is Mg doped titanic acid lithium titanate cathode materials to embodiment moderate multiplying factor performance curve of the invention, and b does not mix
Miscellaneous lithium titanate anode material).
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
Part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
A kind of preparation method of Mg doped titanic acids lithium titanate cathode material, it is characterised in that there are following steps：
S1, according to Li4-xMgxTi5O12Atomic ratio weighs raw material, lithium source excessive 6% respectively, and same dispersant (is put into together
In ball grinder, wherein, Mg comes from Mg compounds, x=0.1-0.3；
S2, ball grinder loaded into ball mill, with 400~600 rotating speed, 1~6h of ball milling；
S3, the liquid after ball milling is placed in drying box, 120 DEG C of dry 12h；Dried powder is combined in into agate mortar
In, grinding is uniform, obtains lithium titanate precursor；
S4, lithium titanate precursor is placed in tube furnace, at 600~900 DEG C, under air atmosphere, be heat-treated after 4~8h
To Mg doped titanic acid lithium titanate cathode materials.
The dispersant is ethanol.
The Mg compounds are Mg (CH3COO)2·4H2O, MgO or Mg (OH)2。
In the present embodiment, the technological parameter of Mg doped titanic acid lithium titanate cathode materials is that Mg compounds are Mg (OH)2, x=0.2,
Rotational speed of ball-mill 400, ball milling 3h, 8h is heat-treated at 800 DEG C；
In the present embodiment, the technological parameter undoped with lithium titanate anode material is rotational speed of ball-mill 400, ball milling 3h, at 800 DEG C
It is heat-treated 8h.
Fig. 1 be the present invention embodiment in XRD test charts (a is Mg doped titanic acid lithium titanate cathode materials, b undoped with
Lithium titanate anode material), it can be seen that doping Mg does not change Li4Ti5O12Structure.
Fig. 2 is that voltage capacitor is bent under the different multiplying undoped with lithium titanate anode material in embodiment of the invention
Line, it can be seen that sample all show stable charge and discharge platform (1.5-1.6V VS Li/Li+), correspond to
Li4Ti5O12Middle Ti4+/Ti3+Redox reaction process.Between the charge and discharge platform that sample can be substantially observed from figure
Difference all increases with being incremented by for discharge-rate.Do not have good voltage platform in 10C undoped with sample.
Fig. 3 is that voltage capacitor is bent under the different multiplying of Mg doped titanic acid lithium titanate cathode materials in embodiment of the invention
Line, it can be seen that sample all show stable charge and discharge platform (1.5-1.6V VS Li/Li+), correspond to
Li4Ti5O12Middle Ti4+/Ti3+Redox reaction process.Between the charge and discharge platform that sample can be substantially observed from figure
Difference all increases with being incremented by for discharge-rate.But the Li after adulterating3.8Mg0.2Ti5O12In 0.57C, charge and discharge platform voltage difference
For 0.06V, even in 10C, charge and discharge platform voltage difference is 0.1V, hence it is evident that less than undoped with sample, illustrates material after adulterating
Electrode polarization degree has obtained significantly declining, and shows Mg2+Doping can improve electrode reaction dynamics.Sample after doping exists
10C still has good voltage platform.
Fig. 4 is that (a is Mg doped titanic acid lithium titanate cathode materials to stable circulation linearity curve, and b is not in embodiment of the invention
Doped titanic acid lithium titanate cathode material), it can be seen that appropriate Mg2+Doping do not destroy itself structure, remain its point
The superperformance of spinel structure, and have enough Ti4+It is changed into Ti3+, improve lacking for itself electron conduction difference
Point, obtained Li3.8Mg0.2Ti5O12With highest first discharge specific capacity, reach 193.6m Ahg-1, than undoped with
Li4Ti5O12First discharge specific capacity 145.3m Ahg-1It is higher by 33.2%.
Fig. 5 is that (a is Mg doped titanic acid lithium titanate cathode materials to embodiment moderate multiplying factor performance curve of the invention, and b does not mix
Miscellaneous lithium titanate anode material), it can be seen that with the increase of discharge-rate, undoped with Li4Ti5O12The capacity of sample
It is quick to reduce, and doped samples possess more preferable capability retention.Even in 10C multiplying powers, it still possesses putting for 125.1mAhg-1
Electric specific capacity, equivalent to 64.6% of specific discharge capacity under initial 0.57C multiplying powers.And undoped with Li4Ti5O12Discharged in 10C
Capacity only has 47.6mAhg-1.When multiplying power turns again to 0.57C, 190.8mAhg-1 specific discharge capacity still can be kept,
Illustrate Li3.8Mg0.2Ti5O12With good invertibity and stability.Mg2+Doping Ti4+ is converted into Ti3+, add electricity
Sub- concentration, this adds increased Li4Ti5O12Electric conductivity, enhance Li+ diffusion.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (3)
1. a kind of preparation method of Mg doped titanic acids lithium titanate cathode material, it is characterised in that there are following steps：
S1, according to Li4-xMgxTi5O12Atomic ratio weighs raw material, lithium source excessive 6% respectively, and is put into ball grinder together with dispersant
In, wherein, Mg comes from Mg compounds, x=0.1-0.3；
S2, ball grinder loaded into ball mill, with 400~600 rotating speed, 1~6h of ball milling；
S3, the liquid after ball milling is placed in drying box, 120 DEG C of dry 12h；Dried powder is combined in agate mortar,
Grinding is uniform, obtains lithium titanate precursor；
S4, lithium titanate precursor is placed in tube furnace, at 600~900 DEG C, under air atmosphere, Mg is obtained after being heat-treated 4~8h
Doped titanic acid lithium titanate cathode material.
A kind of 2. preparation method of Mg doped titanic acids lithium titanate cathode material according to claim 1, it is characterised in that：Described point
Powder is ethanol.
A kind of 3. preparation method of Mg doped titanic acids lithium titanate cathode material according to claim 1, it is characterised in that：The Mg
Compound is Mg (CH3COO)2·4H2O, MgO or Mg (OH)2。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108649213A (en) * | 2018-05-23 | 2018-10-12 | 大连理工大学 | A kind of method that ion doping assisted Solid-state method prepares nano lithium titanate |
| CN109004196A (en) * | 2018-07-24 | 2018-12-14 | 大连理工大学 | A kind of preparation method of cotton cladding lithium titanate anode material |
| CN109216695A (en) * | 2018-08-17 | 2019-01-15 | 安徽赛尔新能源科技有限公司 | A method of 1.55V lithium titanate battery capacity is improved by solid phase reaction |
| CN109301236A (en) * | 2018-08-17 | 2019-02-01 | 中北润良新能源汽车(徐州)股份有限公司 | A kind of solid reaction process improving 1.55V lithium titanate battery capacity |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108649213A (en) * | 2018-05-23 | 2018-10-12 | 大连理工大学 | A kind of method that ion doping assisted Solid-state method prepares nano lithium titanate |
| CN109004196A (en) * | 2018-07-24 | 2018-12-14 | 大连理工大学 | A kind of preparation method of cotton cladding lithium titanate anode material |
| CN109216695A (en) * | 2018-08-17 | 2019-01-15 | 安徽赛尔新能源科技有限公司 | A method of 1.55V lithium titanate battery capacity is improved by solid phase reaction |
| CN109301236A (en) * | 2018-08-17 | 2019-02-01 | 中北润良新能源汽车(徐州)股份有限公司 | A kind of solid reaction process improving 1.55V lithium titanate battery capacity |
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