CN101728517A - Method for preparing surface self-grown titanium nitride conducting film modified lithium titanate - Google Patents
Method for preparing surface self-grown titanium nitride conducting film modified lithium titanate Download PDFInfo
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- CN101728517A CN101728517A CN200910310151A CN200910310151A CN101728517A CN 101728517 A CN101728517 A CN 101728517A CN 200910310151 A CN200910310151 A CN 200910310151A CN 200910310151 A CN200910310151 A CN 200910310151A CN 101728517 A CN101728517 A CN 101728517A
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Abstract
The invention relates to a method for preparing a surface self-grown titanium nitride conducting film modified lithium titanate, which comprises the following steps of: uniformly mixing lithium titanate powder with solid nitrogen source in proportion in a dispersion medium in a mode of ultrasound or ball milling, drying the obtained slurry at the temperature of between70 and 120 DEG C, raising temperature to 600 to 900 DEG C in the inert protective atmosphere after grinding, preserving the heat for 10min to 1h, and then cooling together with a furnace to obtain the surface self-grown titanium nitride conducting film modified lithium titanate. Through heat nitrogen reaction, a layer of high-conductive film TiN is self-grown on the surface of the lithium titanate; the TiN film is firmly combined with the lithium titanate; and the prepared high-conductive Li4Ti5O12/ TiN material has high multiplying power of charge-discharge property and excellent circulating property. The preparation method has the advantages of low cost, simple operation and safety, and easy realization of mass production.
Description
Technical field
The invention belongs to the new energy materials technical field, be specifically related to a kind of lithium ion battery negative material, particularly relate to utilize solid-state nitrogen source by the pyrolysis nitridation reaction in lithium titanate surface self-grown one floor height conductive titanium nitride thin film technique.
Background technology
The world today, along with global petroleum resources anxiety, the air environmental pollution aggravation, hybrid-electric car of energy-conserving and environment-protective (HEV) and pure electric automobile (EV) are current have been received people's concern especially and has developed greatly.And electric automobile is urgent day by day to the demand of the chemical power source of big capacity, high power, high safety.Lithium ion battery becomes one of main power resources of electric automobile with advantages such as its high-energy-density, high working voltage, memory-less effects.At present, commercial lithium ion battery negative material mainly is the graphite-like material with carbon element.Though such material has bigger specific capacity, the embedding lithium current potential that subject matter is carbon electrode and the current potential of lithium metal are very approaching, in the large current charge process, very easily separate out lithium and form dendrite, have potential safety hazard.Simultaneously owing to generate the SEI film on its surface in the carbon negative pole initial charge process, not only consume a large amount of lithium salts, cause irreversible capacity loss, and high temperature causes the SEI film destroy easily, the damaged material structure, cause the decline of battery performance, can't satisfy the requirement of lithium ion battery high current charge-discharge.
Lithium titanate (the Li of spinel structure
4Ti
5O
12) owing to have high Ti
4+/ Ti
3+Therefore (1.55V vs Li) redox potential has than carbon negative pole and the higher fail safe of lithium metal; Do not have the formation of SEI film simultaneously on the lithium titanate surface, also have higher energy conversion efficiency; The theoretical specific capacity of lithium titanate is 175mAh/g, is a kind of Yao Wen P Diao material, the characteristics that volume changes hardly in the charge and discharge process, make its as the cycle life of lithium ion battery negative material up to 4000 times, apparently higher than graphite cathode.Lithium titanate makes it become the negative material that lithium ion battery has development prospect with its excellent cycle performance, charging and discharging capabilities and advantage such as charging/discharging voltage platform stably, and huge researching value and commercial application prospect are arranged.
Yet, because Li
4Ti
5O
12The intrinsic electronic conductivity of material is lower by (about 10
-13S/cm), Li
4Ti
5O
12Capacity attenuation is fast when high current charge-discharge, high rate performance is poor, has limited its application under the high current charge-discharge condition, and therefore improving its high rate performance becomes Li
4Ti
5O
12The key of practicalization.
To Li
4Ti
5O
12The high thing phase of electronic conductivity is introduced on the surface, is coated on particle surface to strengthen the intergranular electron conduction ability of principal phase, improves the electric conductivity of material, is the effective ways that improve the material high rate performance.Carbon coats Li
4Ti
5O
12Be the more a kind of conductivity means that improve electrode material of current employing, at Li
4Ti
5O
12Add carbon source in the preparation process, thereby disperse or coated with conductive carbon at particle surface.On the one hand, stoping material granule to be reunited in calcination process grows up; On the other hand, make up conductive network, improve material conductivity, improve Li then
4Ti
5O
12High rate performance.But too much carbon will reduce the specific discharge capacity and the tap density of material, and carbon coating layer is difficult at Li simultaneously
4Ti
5O
12It is even, firm that particle surface coats, and causes unstable properties.
Therefore, explore novel Li
4Ti
5O
12It is particularly important that surface modification method just seems.TiN has good electrical conductivity, thermal conductivity, stability, and the lining material of inner lining material, electric contact and metal material that is widely used in the molten-salt electrolysis metal is first-class.The researcher adopts at Li
4Ti
5O
12Material surface coated with conductive agent TiN (conductivity 1 * 10
4~4 * 10
4S/cm), the structure conductive network increases the electron conduction ability between the particle, improves electronic conductivity, improves the high current charge-discharge multiplying power property then.Snyder M Q (Journal of Power Sources, 2007,165 (1): 379-385.) waited by atomic layer deposition method (ALD) at Li in 2007
4Ti
5O
12Surface deposition one deck TiN makes Li
4Ti
5O
12Conductivity be improved.Samsung company (J.Am.Chem.Soc., 2008,130 (45): 14930-14931.) pass through hot ammonia gas react at Li in report in 2008
4Ti
5O
12Superficial growth one deck TiN film, demonstrated excellent multiplying power property.Above-mentioned two kinds of methods and the present invention make a marked difference, and atomic layer deposition method is to utilize TiCl
4Gas and NH
3Gas is at lithium titanate particle surface depositing TiN monoatomic layer.This method complicated operation, cost is higher, and condition is difficult to control.The ammonia gas react method of Samsung company is by hot NH
3Gas and Li
4Ti
5O
12Be reflected at Li
4Ti
5O
12The surface obtains TiN, and this method uses ammonia to have danger, severe corrosive, and environment is unfriendly, and is difficult to guarantee the homogeneity of material coating.
Summary of the invention
At Li
4Ti
5O
12The problem of the electronic conductivity difference of material own the objective of the invention is to propose a kind of preparation method of surface self-grown titanium nitride conducting film modified lithium titanate, can prepare the good Li of high-rate charge-discharge capability
4Ti
5O
12/ TiN nucleocapsid electrode material improves the electron conduction ability of material.The present invention is by the pyrolysis nitridation reaction, at lithium titanate surface self-grown one floor height conductive film TiN, the TiN film not only with lithium titanate in conjunction with close and firm, and the height of preparation conduction Li
4Ti
5O
12/ TiN material has high rate charge-discharge performance and excellent cycle performance, and its preparation method is with low cost, simple to operate, safe, accomplish scale production easily.
Because the mechanism and the NH of solid-state nitrogenous source and lithium titanate pyrolysis nitridation reaction
3Machine-processed different with the hot ammonia react of lithium titanate are nanoscale and uniformity in order to guarantee self-growing conducting film, the conductivity of electrolyte materials height.Therefore, it will be particularly important selecting suitable solid nitrogenous source, and the content of the structure of nitrogenous source material, composition, nitrogenous source will influence deposition rate, conductivity and the bond strength of product on the lithium titanate surface simultaneously; Reaction temperature, reaction time and mixing procedure etc. will have a strong impact on the effect of coating and the performance of material simultaneously.
The objective of the invention is to realize in the following manner.
A kind of lithium ion battery may further comprise the steps with the preparation method of surface self-grown titanium nitride conducting film modified lithium titanate:
With lithium titanate powder and solid-state nitrogenous source in proportion in decentralized medium ultrasonic or ball milling mix, after 70~120 ℃ of oven dry of slurry of making, grinding, at inertia protection gas (preferred N
2) under the atmosphere, being warming up to 600~900 ℃ (preferred especially 700~850 ℃), insulation 10min~1h with the stove cooling, obtains surface self-grown titanium nitride conducting film modified lithium titanate then.
The temperature range that the present invention established is the temperature range that the solid-state nitrogenous source cracking chemical reaction of the present invention generates the suitable technology of the present invention of TiN.Cross the low temperature TiN that can't grow certainly, too high temperature can cause the particle agglomeration growth, reduces the performance of material.In addition, reaction temperature retention time among the present invention and mixing procedure determines that can guarantee effectively that self-growing conducting film is nanoscale and uniformity, conductivity of electrolyte materials is high again, has charge-discharge performance well.
Used solid-state nitrogenous source is one or more in urea, biuret, cyanamide, cyanamid dimerization, melamine, ammelide, the ammeline among the preparation method of described surface self-grown titanium nitride conducting film modified lithium titanate.The present invention preferentially selects urea, and this cost of material is cheap, safety is easy to get, and it decomposes intermediate product and lithium titanate generates TiN in pyroreaction.
The addition of solid-state nitrogenous source is the 1-20wt% of lithium titanate.The optimal addn of solid-state nitrogenous source is the 2-10wt% of lithium titanate.The nitrogenous source that adds this scope will help the lithium titanate surface to form the nano level conducting film of one deck, simultaneously the content of conducting film account for the content of whole lithium titanate can not be too high, the too high specific capacity that will reduce the entire electrode material influences its application in lithium ion battery then.The content of nitrogenous source is crossed to hang down and can't be formed a certain amount of conducting film, and the electric conductivity of lithium titanate improves not obvious, and the high rate performance to battery material can't improve then.
Decentralized medium is one or more in ethanol, water, acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, the n-heptanol; Wherein preferred water, ethanol.The solvent raw material cheaply is easy to get, volatilizees easily, does not exist pollution, can well dissolve solid-state nitrogenous source again simultaneously, guarantees that raw material mixes.
Lithium titanate powder composition Li
4Ti
5-xM
xO
12Perhaps Li
4-yM
yTi
5O
12Wherein M is Cr, Fe, Al, Pr or Ni, 0≤X≤0.5,0≤Y≤0.33
Atmosphere furnace heats up with the speed of 2~5 ℃/min.
Method of the present invention is to compare with the ammonia gas react method of Samsung company, because Samsung company is by hot NH
3Gas and Li
4Ti
5O
12Be reflected at Li
4Ti
5O
12The surface obtains TiN, and this method uses ammonia to have danger, severe corrosive, and environment is unfriendly, and is difficult to guarantee the homogeneity of material coating.And the present invention be by with Li
4Ti
5O
12The solid-state nitrogenous source thermal decomposition that mixes obtains nitrogenous intermediate and Li
4Ti
5O
12Be reflected at its surface self-grown TiN conducting film, the present invention has not only avoided using the danger of ammonia and the complexity of operation, and the reaction homogeneous, and (ALD is with low cost, easier accomplishing scale production than atomic layer deposition method.
Lithium ion battery of the present invention is reflected at lithium titanate surface self-grown one floor height conductive titanium nitride film with the preparation method of the surface self-grown titanium nitride conducting film modified lithium titanate hot nitrogen by solid-state nitrogenous source, this layer film contacts more firm tight with the lithium titanate material surface, thereby can improve the electron conduction ability of material greatly, effectively improve the high rate charge-discharge performance of material.
Description of drawings
Fig. 1 is Li
4Ti
5O
12The XRD figure of/TiN material.
Fig. 2 is Li
4Ti
5O
12The TEM figure of/TiN material.
Fig. 3 is Li
4Ti
5O
12/ TiN and Li
4Ti
5O
12The high rate performance correlation curve of material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.
Embodiment 1
Press urea: Li
4Ti
5O
12Mass ratio is 5% adding urea 1.23g, and ball milling mixing 2h in the anhydrous ethanol medium puts into 70 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 2 ℃/min under the protective atmosphere is warming up to 800 ℃ of insulation 30min, cools off with stove then.Products therefrom is Li
4Ti
5O
12/ TiN combination electrode material.
Material property characterizes:
The crystal structure of Japan Rigaku 3014 type X-ray diffractometer analysis of material is with the pattern of transmission electron microscope TEM (PhilipsCM12) observation material.
Electrochemical property test:
Electrode slice is with assembling all prepares as follows to the lithium half-cell: with embodiment 1 prepared Li
4Ti
5O
12/ TiN combination electrode material, conductive black, binding agent evenly mix according to mass ratio at 8: 1: 1, drip an amount of solvent (NMP), after fully grinding slurry evenly is coated on the 10 μ m Copper Foil collectors, 120 ℃ of following vacuumize 12h strike out diameter and are the electrode thin slice about 1cm then.In being full of the glove box of argon gas work electrode, barrier film, metal lithium sheet be assembled into the lithium half-cell is carried out electrochemical property test, barrier film is Celgard 2400, and electrolyte is 1.2mol LiPF
6/ EC-DMC-EMC, wherein: EC: DMC: EMC=1: 1: 1 (W/W).
Take out the back and carry out the constant current charge and discharge with blue electricity (LAND) series battery test macro and test, the test voltage scope is 0.8~2.5V, with a certain multiplying power electric current constant-current discharge to 0.8V, again with same electric current constant current charge to 2.5V.
XRD detects and is spinelle Li
4Ti
5O
12Characteristic peak, as Fig. 1.It is the uniform submicron particles of particle diameter that transmission electron microscope can be observed lithium titanate, and surperficial coating layer with nm level, as Fig. 2.
Press the Li of embodiment 1 method and proportioning preparation
4Ti
5O
12Gram volume is 164mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 162.1mAh/g under the 0.5C charging and discharging currents, and gram volume is 131mAh/g under the 3C charging and discharging currents, as Fig. 3.Capability retention 〉=95% of 100 of material circulations when 1C discharges and recharges.
Press urea: Li
4Ti
5O
12Mass ratio is 3% adding urea 0.74g, and ultrasonic mixing 1h in the anhydrous ethanol medium puts into 100 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 5 ℃/min under the protective atmosphere is warming up to 850 ℃ of insulation 30min, cools off with stove then.Products therefrom is Li
4Ti
5O
12/ TiN combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 2 methods and proportioning preparation
4Ti
5O
12Gram volume is 160.4mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 159.3mAh/g under the 0.5C charging and discharging currents, and gram volume is 130mAh/g under the 3C charging and discharging currents.Capability retention 〉=94% of 100 of material circulations when 1C discharges and recharges.
Embodiment 3
Press urea: Li
4Ti
5O
12Mass ratio is 10% adding urea 2.5g, and ball milling mixing 2h in medium-acetone puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 3 ℃/min under the protective atmosphere is warming up to 850 ℃ of insulation 10min, cools off with stove then.Products therefrom is Li
4Ti
5O
12/ TiN combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 3 methods and proportioning preparation
4Ti
5O
12Gram volume is 159.5mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 158.1mAh/g under the 0.5C charging and discharging currents, and gram volume is 125mAh/g under the 3C charging and discharging currents.Capability retention 〉=92% of 100 of material circulations when 1C discharges and recharges.
Press melamine: Li
4Ti
5O
12Mass ratio is 2% adding urea 0.5g, is ball milling mixing 2h in the medium at isopropyl alcohol, puts into 80 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 3 ℃/min under the protective atmosphere is warming up to 700 ℃ of insulation 20min, cools off with stove then.Products therefrom is Li
4Ti
5O
12/ TiN combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 4 methods and proportioning preparation
4Ti
5O
12Gram volume is 166.4mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 163.3mAh/g under the 0.5C charging and discharging currents, and gram volume is 140.1mAh/g under the 3C charging and discharging currents.Capability retention 〉=96% of 100 of material circulations when 1C discharges and recharges.
Embodiment 5
Press urea: Li
4Ti
5O
12Mass ratio is 6% adding urea 1.5g, and ball milling mixing 2h in the anhydrous ethanol medium puts into 90 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 5 ℃/min under the protective atmosphere is warming up to 800 ℃ of insulation 40min, cools off with stove then.Products therefrom is Li
4Ti
5O
12/ TiN combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 5 methods and proportioning preparation
4Ti
5O
12Gram volume is 162.9mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 161.5mAh/g under the 0.5C charging and discharging currents, and gram volume is 135mAh/g under the 3C charging and discharging currents.Capability retention 〉=95% of 100 of material circulations when 1C discharges and recharges.
Embodiment 6
Press urea: Li
4Ti
5O
12Mass ratio is 5% adding urea 1.23g, is ball milling mixing 2h in the medium with water, puts into 70 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 3 ℃/min under the protective atmosphere is warming up to 900 ℃ of insulation 10min, cools off with stove then.Products therefrom is Li
4Ti
5O
12/ TiN combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 6 methods and proportioning preparation
4Ti
5O
12Gram volume is 165.2mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 163.8mAh/g under the 0.5C charging and discharging currents, and gram volume is 142.3mAh/g under the 3C charging and discharging currents.Capability retention 〉=94% of 100 of material circulations when 1C discharges and recharges.
Embodiment 7
Press urea: Li
3.75Mg
0.25Ti
5O
12Mass ratio is 5% adding urea 1.3g, and ball milling mixing 2h in the anhydrous ethanol medium puts into 80 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 5 ℃/min under the protective atmosphere is warming up to 850 ℃ of insulation 15min, cools off with stove then.Products therefrom is Li
3.75Mg
0.25Ti
5O
12/ TiN combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 7 methods and proportioning preparation
3.75Mg
0.25Ti
5O
12Gram volume is 153.2mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 120.2mAh/g under the 0.5C charging and discharging currents, and gram volume is 90.2mAh/g under the 3C charging and discharging currents.Capability retention 〉=89.2% of 100 of material circulations when 1C discharges and recharges.
Embodiment 8
Press urea: Li
4Al
0.15Ti
4.85O
12Mass ratio is 2% adding urea 0.6g, and ball milling mixing 2h in the anhydrous ethanol medium puts into 100 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Speed with 4 ℃/min under the protective atmosphere is warming up to 800 ℃ of insulation 60min, cools off with stove then.Products therefrom is Li
4Al
0.15Ti
4.85O
12/ TiN combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 8 methods and proportioning preparation
4Al
0.15Ti
4.85O
12Gram volume is 150.4mAh/g under the/TiN combination electrode material 0.2C charging and discharging currents, and gram volume is 130.9mAh/g under the 0.5C charging and discharging currents, and gram volume is 100.2mAh/g under the 3C charging and discharging currents.Capability retention 〉=85% of 100 of material circulations when 1C discharges and recharges.
Claims (6)
1. the preparation method of a surface self-grown titanium nitride conducting film modified lithium titanate; it is characterized in that may further comprise the steps: the addition in solid-state nitrogenous source is the 1-20% ratio of lithium titanate weight; lithium titanate powder and solid-state nitrogenous source ultrasonic or ball milling in decentralized medium is mixed; after 70~120 ℃ of oven dry of slurry of making, grinding; under the inertia protective atmosphere; be warming up to 600~900 ℃ of insulation 10min~1h; with the stove cooling, obtain surface self-grown titanium nitride conducting film modified lithium titanate then.
2. the preparation method of a kind of surface self-grown titanium nitride conducting film modified lithium titanate according to claim 1, it is characterized in that: solid-state nitrogenous source is one or more in urea, biuret, cyanamide, cyanamid dimerization, melamine, ammelide, the ammeline.
3. the preparation method of a kind of surface self-grown titanium nitride conducting film modified lithium titanate according to claim 1, it is characterized in that: the addition of solid-state nitrogenous source is the 2-10% of lithium titanate weight.
4. the preparation method of a kind of surface self-grown titanium nitride conducting film modified lithium titanate according to claim 1, it is characterized in that: decentralized medium is one or more in ethanol, water, acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, the n-heptanol.
5. the preparation method of a kind of surface self-grown titanium nitride conducting film modified lithium titanate according to claim 1 is characterized in that: lithium titanate powder composition Li4Ti5-xMxO12 or Li4-yMyTi5O12; Wherein M is Cr, Fe, Al, Pr or Ni, 0≤X≤0.5,0≤Y≤0.33.
6. the preparation method of a kind of surface self-grown titanium nitride conducting film modified lithium titanate according to claim 1 is characterized in that: atmosphere furnace heats up with the speed of 2~5 ℃/min.
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US9531004B2 (en) | 2013-12-23 | 2016-12-27 | GM Global Technology Operations LLC | Multifunctional hybrid coatings for electrodes made by atomic layer deposition techniques |
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CN107799755A (en) * | 2017-10-31 | 2018-03-13 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of lithium titanate particle Surface coating titanium nitride |
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