CN102569767B - Polymer composite lithium titanate electrode material and preparation method thereof - Google Patents
Polymer composite lithium titanate electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polymer composite lithium titanate electrode material and a preparation method thereof. The method comprises the following steps of: (1) preparing an oxidant solution A and a protonic acid solution B of a polymer monomer; and (2) adding lithium titanate powder into the solution B, and dropwise adding the solution A into the solution B gradually, performing mechanical stirring under the ultrasonic condition for reaction, and washing and drying the obtained product to obtain the polymer composite lithium titanate electrode material. Compared with the traditional mechanical mixing method, the method provided by the invention has better composite effect, and effective combination is formed on the molecular level; the electric conductivity of the prepared electrode material can be improved to more than 10<-1>S/cm magnitude of lithium titanate from the 10<-9>S/cm magnitude of lithium titanate; and the high-current charge/discharge performance of lithium titanate is greatly improved.
Description
Technical field
The invention belongs to electrode material preparation field, particularly, the present invention relates to a kind of polymer composite lithium titanate electrode and preparation method thereof.
Background technology
Lithium ion battery, as a kind of novel energy-storing device, has operating voltage high, and specific energy is large, and the advantages such as service life cycle is long, and self discharge is little, and operating temperature range is wide, and fail safe is good, memory-less effect, nuisanceless, are subject to extensive concern in recent years.Ultracapacitor is another kind of novel energy-storing device, have can be comparable with battery energy storage capacity.And compared with battery, ultracapacitor discharge and recharge is faster, there is stronger high power discharge ability, thus have broad application prospects equally.
Lithium titanate (Li
4ti
5o
12), lithium-titanium composite oxide, there is spinel structure, 20 century 70s are carried out large quantity research by as superconduction, the end of the eighties, the positive electrode of Zeng Zuowei lithium ion battery was studied, but because its and energy density on the low side relative to lithium current potential is also lower (theoretical capacity is 175mAh/g), and fail to cause the extensive concern of people.1996, in primary electrochemical meeting, Canadian Studies person K.Zaghib proposes to adopt lithium titanate material to make negative material first and high-voltage anode forms lithium ion battery, forms asymmetric super-capacitor with carbon electrode.Afterwards, little bavin letter was fine waits people also to it can be used as ion cathode material lithium to carry out research.But until before and after 1999, people just start large quantifier elimination to spinel lithium titanium compound as the negative material of lithium ion battery.
Lithium titanate (Li
4ti
5o
12) as a kind of novel intercalation materials of li ions, can use as negative material in lithium ion battery and asymmetric super-capacitor.Its embedding lithium reaction equation is:
3Li+Li
4Ti
5O
12→Li
7Ti
5O
12
This reaction normal electrode potential is 1.56V, and therefore lithium titanate can be used as negative material, forms lithium ion battery, also can form asymmetrical type ultracapacitor with active carbon positive pole with positive electrode material such as type such as 4V such as cobalt acid lithium, LiMn2O4 etc.The embedding that its advantage is lithium with deviate from lithium titanate lattice dimensions in process and change hardly, avoid the change in volume in charge and discharge circulation, thus can capacity attenuation be avoided, extend cell integrated useful life.
Lithium titanate is its electronic conductivity too low (only 10 as the major defect that electrode material exists
-9s/cm magnitude) therefore to improve conductivity, the important directions that high power discharge performance is research is always improved to its modification.
In solid-state physics, embedding refers to that moveable object particle (molecule, atom, ion) is reversibly embedded on the network lattice vacancy of the host lattice with suitable dimension, during embedded ion, require that host lattice makees charge compensation, to maintain electric neutrality, change by host lattice band structure realizes by charge compensation, so conductivity can change before and after particle embeds.In lithium-ions battery, the new Li inserted
+be fill out on gap, suffered active force is much little, and conductivity can increase substantially.Therefore, want the ionic conductivity improving material, must manage to reduce the active force between migration ion and main framing, and have enough large passage to Ion transfer.The valence state of main framing can be caused uneven by doping introducing high price or low price element, thus produce new space or increase migration ion concentration, doping is also by improving the stability of main framing, on purpose manufacture the size of hole or change passage, reduction skeleton and interionic active force are beneficial to the migration of ion, thus improve the conductivity of ion.
Another factor affecting electrochemical kinetics is exactly the electronic conductivity of material.When charge and discharge cycles, electronics with the insertion of lithium ion and must be deviate from.If material electronics can not import in time and derive, then the diffusion of lithium ion inevitable replace by the transfer rate of electronics.The electronics of enrichment by by polarity effect conversely limiting lithium ion insertion and deviate from and material electrochemical performance worsened.And doping vario-property, constructing a conduction by introducing conductive additive soaks into net, electronic conductivity can be improved several orders of magnitude, increases the energy content of battery, realizes fast charging and discharging.
Doping vario-property mainly can be realized by two aspects: (1) carbon doping is coated; (2) doped with metal elements.
CN 102001701A discloses a kind of preparation method of carbon-coated nano lithium titanate material.First it utilize chemical vapour deposition technique, adopt gas organic compound, at TiO 2 precursor coated with uniform one deck carbon, and by controlling the temperature of chemical vapour deposition (CVD), the throughput of time and rich carbon gas realizes in TiO 2 precursor coated with uniform conductive carbon layer, and then carbon drop clad nano titanium dioxide mixes with the stoichiometric proportion of lithium salts according to Li/Ti=0.82, sinter under inert atmosphere protection, obtained carbon-coated nano lithium titanate material, just effectively overcome the problem of the large and pure phase lithium titanate material electron conduction rate variance of material particle size prepared by conventional solid, there is excellent chemical property, the polarization of material reduces greatly, doubly forthrightly obtain effective raising, and stable cycle performance, simultaneously, preparation method's technological process of the present invention is simple, be easy to accomplish scale production.
CN 102054963A discloses a kind of negative electrode of lithium titanate battery material containing rare metal, and it comprises the lithium titanate material of synthesis, wherein: containing one or more yttriums in described lithium titanate material; Yttrium is Zr, Al, La, Ce, Pr, Nd, Sm, Dy or Ho; Yttrium content presses oxide basis, and content is 0.01 ~ 3wt%; In lithium titanate material, lithium titanium mol ratio is 0.7 ~ 1.2; The operations such as employing batch mixing, ball milling sieve, high-temperature process, secondary ball milling, soak are produced.This invention is containing the negative electrode of lithium titanate battery material of yttrium, and adulterate yttrium, and improve fast charging and discharging performance, improve electrochemistry capacitance, cycle performance excellence, favorable reproducibility, consistency are high; And raw material is cheap, generated time is short, and temperature is low, low for equipment requirements, and preparation technology is simple, is applicable to industrial-scale production.
Bahloul etc. are at β-MnO
2the polymerization of polythiophene monomer is carried out on surface, prepares polythiophene-manganese dioxide composite electrode to improve the conductivity (A.Bahloul, B.Nessark, F.Habelhames and C.M.Julien, Ionics 2011,17,239-246.) of manganese dioxide.And US Patent No. 2011/0262800A1 discloses doping B, P, the mode of Na and K carries out modification to lithium titanate material.But have no report in the method for lithium titanate surface composite conductive polymer.
Summary of the invention
An object of the present invention is the preparation method providing a kind of polymer composite lithium titanate electrode.Described method carries out polymerization reaction while adopting polymer monomer to mix with lithium titanate is ultrasonic, obtains the lithium titanate composite material of even coated with conductive polymer.The described method reaction time is short, and reaction temperature is low, low for equipment requirements, and preparation technology is simple, is applicable to industrial-scale production.
In order to reach above object, present invention employs following technical scheme:
The preparation method of polymer composite lithium titanate electrode, it comprises the following steps:
(1) solution A of oxidant is prepared, the protonic acid solution B of prepared polymer monomer;
(2) lithium titanate powder is added in solution B, then solution A is progressively added drop-wise in solution B, under ultrasound condition, carry out mechanical agitation, react, obtain product;
(3) by above-mentioned product washing, drying, polymer composite lithium titanate electrode is obtained.
Conducting polymer, also known as conducting polymer, refers to by means such as doping, can make the polymer of conductivity within the scope of semiconductor and conductor.Containing singly-bound alternately and double bond on this base polymer main chain, thus define large conjugated pi system.The flowing of pi-electron creates the possibility of conduction.
The present invention adopts chemical oxidising polymerisation to obtain conducting polymer.Its synthesis mechanism is as described below: first, and under the effect of oxidant, an electroneutral conducting polymer monomer molecule loses an electronics and is oxidized to radical cation.Then, two radical cations combine the dication generating dimer, and this dication, through disproportionation, generates electroneutral dimer.Then, dimer is oxidized again, is combined with radical cation, then disproportionation, generates tripolymer, and reaction is gone down like this, until generating polymer is the conducting polymer of n.
The oxidant of what those skilled in the art can be known can be used for preparing conducting polymer all can realize the present invention.Preferably, oxidant of the present invention is selected from the combination of a kind of in potassium peroxydisulfate, ammonium persulfate, ferric trichloride, hydrogen peroxide or at least two kinds.The combination of described combination such as potassium peroxydisulfate and ammonium persulfate, the combination of ferric trichloride and hydrogen peroxide, the combination of potassium peroxydisulfate and ferric trichloride, the combination of potassium peroxydisulfate and hydrogen peroxide, the combination of potassium peroxydisulfate, ammonium persulfate, ferric trichloride, the combination of ammonium persulfate, ferric trichloride, hydrogen peroxide.
Those skilled in the art according to the solvent of common practise selective oxidation agent solution, can reach and make oxidant uniform dissolution obtain finely dispersed oxidizing agent solution in a solvent.
Preferably, described conducting polymer monomer is selected from the combination of a kind of in aniline, pyrroles, thiophene, acetylene or at least two kinds, the combination of described combination such as aniline and pyrroles, the combination of aniline and thiophene, the combination of aniline and acetylene, the combination of pyrroles, thiophene, acetylene, the combination of aniline, thiophene, acetylene.The combination of a kind of in the preferred aniline of described conducting polymer monomer, pyrroles, thiophene or at least two kinds.
Conducting polymer only has after overdoping, just can present good electric conductivity.By protonic acid, obtain the conducting polymer of doping state, the conductivity of conducting polymer can be improved.The electric charge that the mixing of Bronsted acid makes in conductive polymer molecules and intermolecular conformation is more conducive on strand is delocalized, and conductivity increases substantially.Bronsted acid of the present invention is selected from the combination of a kind of in hydrochloric acid, sulfuric acid, nitric acid or at least two kinds, the combination of described combination such as hydrochloric acid and sulfuric acid, the combination of hydrochloric acid and nitric acid, the combination of sulfuric acid and nitric acid.Those skilled in the art can select the concentration of described Bronsted acid voluntarily according to this area knowledge.
Preferably the concentration of the protonic acid solution of described conductive polymer monomer is 0.02 ~ 5mol/L, such as 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 5mol/L, 4.9mol/L, 4.8mol/L, 4.7mol/L, 4.6mol/L, 4.5mol/L, 4.4mol/L, 4.3mol/L, 4.2mol/L, 4.1mol/L, preferably 0.04 ~ 4mol/L, further preferred 0.05 ~ 3mol/L.
Preferably, described lithium titanate is 1: 1 ~ 10 with the ratio of the amount of substance of conducting polymer monomer, such as 1: 1.1,1: 1.2,1: 1.3,1: 1.4,1: 1.5,1: 1.6,1: 1.7,1: 1.8,1: 1.9,1: 2,1: 2.2,1: 2.4,1: 2.6,1: 2.8,1: 9.8,1: 9.6,1: 9.4,1: 9.2,1: 9.0,1: 8.8,1: 8.6,1: 8.4,1: 8.2,1: 8, preferably 1: 3 ~ 8, further preferably 1: 4.
Preferably, described oxidant is 1: 0.25 ~ 6 with the ratio of the amount of substance of polymer monomer, such as 1: 0.3,1: 0.4,1: 0.5,1: 0.6,1: 0.7,1: 0.8,1: 0.9,1: 5.8,1: 5.6,1: 5.4,1: 5.2,1: 5.0,1: 4.8,1: 4.6,1: 4.4,1: 4.2,1: 4.0, preferably 1: 1 ~ 6, further preferably 1: 2.
Preferably, described ultrasonic frequency is 20 ~ 50kHz, such as 21kHz, 22kHz, 23kHz, 24kHz, 25kHz, 26kHz, 27kHz, 28kHz, 29kHz, 49kHz, 48kHz, 47kHz, 46kHz, 45kHz, 44kHz, 43kHz, 42kHz, 41kHz, preferred 40kHz.
The knowledge that those skilled in the art can grasp according to it and experience select churned mechanically mode voluntarily.
Preferably, the temperature of described reaction is 0 ~ 120 DEG C, such as 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 15 DEG C, 25 DEG C, 35 DEG C, 45 DEG C, 55 DEG C, 65 DEG C, 75 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, preferably 0 ~ 100 DEG C, preferably 0 ~ 80 DEG C further.Wherein, temperature is 0 DEG C, represents that the temperature of described reaction is 0 DEG C.
The knowledge that those skilled in the art can grasp according to oneself and common sense select the speed progressively dripped, and the present invention is not restricted this.
Preferably, the time of described reaction is 1 ~ 30h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 29h, 28h, 27h, 26h, 25h, preferably 1.5 ~ 28h, further preferred 2 ~ 24h.
Preferably, described washing adopts water and organic solvent to carry out; Described water is preferably deionized water; Described organic solvent is selected from the combination of a kind of in acetone, ethanol, ether or at least two kinds, the combination of described combination such as acetone and ether, the combination of acetone and ethanol, the combination of ethanol and ether.
Preferably, described drying is selected from forced air drying, vacuumize, microwave drying, the combination of a kind of in infrared drying or at least two kinds, described combination such as forced air drying and vacuum drying combination, the combination of forced air drying and microwave drying, the combination of forced air drying and infrared drying, the combination of vacuumize and microwave drying, the combination of vacuumize and infrared drying, preferred vacuumize, described vacuum drying temperature is 35 ~ 150 DEG C, such as 36 DEG C, 37 DEG C, 38 DEG C, 39 DEG C, 45 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, preferably 40 ~ 130 DEG C, preferably 40 ~ 120 DEG C further,
Preferably, the described vacuum drying time is 18 ~ 30h, such as 18.5h, 19h, 19.5h, 20.5h, 21h, 21.5h, 29.5h, 28.5h, 29h, 28h, 27.5h, 27h, 26.5h, preferably 20 ~ 26h, further preferred 24h.
Another object of the present invention is to provide a kind of polymer composite lithium titanate electrode, it is prepared by method described above.
The polymer lithium titanate electrode material prepared by the present invention has important purposes as negative material.It can be used as the negative material in lithium ion battery or ultracapacitor, can significantly improve the charge-discharge performance of lithium ion battery or ultracapacitor, extends battery.
Compared with prior art, the present invention has following technique effect:
(1) the present invention carries out doping vario-property by coated with conductive polymer to lithium titanate, polymerization reaction is carried out while adopting conducting polymer monomer to mix with lithium titanate is ultrasonic, obtain the lithium titanate composite material of even coated with conductive polymer, construct a conduction and soak into net, improve electronic conductivity, increase the energy content of battery, realize fast charging and discharging.
(2) the present invention has better composite effect relative to traditional mechanical mixing, is formed with the combination of effect in molecule aspect, and the electrode material conductivity made can by 10 of lithium titanate
-9s/cm magnitude brings up to 10
-1more than S/cm, substantially improves the high current charge-discharge electrical property of lithium titanate.
(3) the method for the invention reaction time is short, and reaction temperature is low, low for equipment requirements, and preparation technology is simple, is applicable to industrial-scale production.
Polymer composite lithium titanate electrode provided by the invention and preparation method thereof as discussed in the summary of the invention section.Description by following embodiment is illustrated substantive distinguishing features of the present invention and marked improvement by the present invention further, but the present invention is not only confined to following embodiment.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
(1) be dissolved in 100mL water by the oxidant potassium peroxydisulfate of 0.02mol, wiring solution-forming A, be dissolved in by 0.005mol pyrrole monomer in the hydrochloric acid of 100mL 1mol/L, wiring solution-forming B, now in two solution, the mol ratio of potassium peroxydisulfate and pyrrole monomer is 4: 1;
(2) 0.005mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 1 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 40kHz ultrasound environments, constant temperature 30 DEG C reaction 6h, product is filtered, and with deionized water and acetone cyclic washing product, until filtrate is colourless, by the product vacuumize 24h at 60 DEG C after washing, obtain polymer composite titanic acid lithium material.
Embodiment 2
(1) be dissolved in 100mL water by the oxidant ammonium persulfate of 0.02mol, wiring solution-forming A, be dissolved in by 0.02mol pyrrole monomer in the sulfuric acid of 100mL 0.5mol/L, wiring solution-forming B, now in two solution, the mol ratio of ammonium persulfate and pyrrole monomer is 1: 1;
(2) 0.005mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 4 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 40kHz ultrasound environments, constant temperature 0 DEG C reaction 24h, product is filtered, and with deionized water and ether cyclic washing product, until filtrate is colourless, by the product vacuumize 24h at 40 DEG C after washing, obtain polymer composite titanic acid lithium material.
Embodiment 3
(1) be dissolved in 100mL water by the oxidant ferric trichloride of 0.02mol, wiring solution-forming A, be dissolved in by 0.04mol aniline monomer in the nitric acid of 100mL 1mol/L, wiring solution-forming B, now in two solution, the mol ratio of ferric trichloride and aniline monomer is 1: 2;
(2) 0.01mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 4 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 40kHz ultrasound environments, constant temperature 50 DEG C reaction 6h, product is filtered, and with deionized water and ethanol cyclic washing product, until filtrate is colourless, by the product vacuumize 24h at 80 DEG C after washing, obtain polymer composite titanic acid lithium material.
Embodiment 4
(1) be dissolved in 100mL water by the oxidants hydrogen peroxide of 0.02mol, wiring solution-forming A, be dissolved in by 0.06mol thiophene monomer in the hydrochloric acid of 100mL 1mol/L, wiring solution-forming B, now in two solution, the mol ratio of hydrogen peroxide and thiophene monomer is 1: 3;
(2) 0.01mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 6 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 40kHz ultrasound environments, constant temperature 60 DEG C reaction 4h, product is filtered, and with deionized water and ethanol cyclic washing product, until filtrate is colourless, by the product vacuumize 24h at 80 DEG C after washing, obtain polymer composite titanic acid lithium material.
Embodiment 5
(1) be dissolved in 100mL water by the oxidant ammonium persulfate of 0.02mol, wiring solution-forming A, be dissolved in by 0.12mol aniline monomer in the sulfuric acid of 100mL 0.5mol/L, wiring solution-forming B, now in two solution, the mol ratio of ammonium persulfate and aniline monomer is 1: 6;
(2) 0.012mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 10 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 40kHz ultrasound environments, constant temperature 80 DEG C reaction 2h, product is filtered, and with deionized water and ethanol cyclic washing product, until filtrate is colourless, by the product vacuumize 24h at 120 DEG C after washing, obtain polymer composite titanic acid lithium material.
Embodiment 6
(1) be dissolved in 100mL water by the oxidant ammonium persulfate of 0.01mol, wiring solution-forming A, be dissolved in by 0.004mol thiophene monomer in the hydrochloric acid of 200mL 1mol/L, wiring solution-forming B, now in two solution, the mol ratio of ammonium persulfate and thiophene monomer is 1: 0.4;
(2) 0.004mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 1 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 20kHz ultrasound environments, constant temperature 120 DEG C reaction 1h, product is filtered, and with deionized water and ethanol cyclic washing product, until filtrate is colourless, by the product vacuumize 30h at 35 DEG C after washing, obtain polymer composite titanic acid lithium material.
Embodiment 7
(1) be dissolved in 100mL water by the oxidant ammonium persulfate of 0.02mol, wiring solution-forming A, be dissolved in by 0.12mol aniline monomer in the sulfuric acid of 100mL 0.5mol/L, wiring solution-forming B, now in two solution, the mol ratio of ammonium persulfate and aniline monomer is 1: 6;
(2) 0.012mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 10 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 50kHz ultrasound environments, constant temperature 10 DEG C reaction 30h, product is filtered, and with deionized water and ethanol cyclic washing product, until filtrate is colourless, by the product vacuumize 18h at 150 DEG C after washing, obtain polymer composite titanic acid lithium material.
Embodiment 8
(1) be dissolved in 100mL water by the oxidant ferric trichloride of 0.02mol, wiring solution-forming A, be dissolved in by 0.04mol aniline monomer in the nitric acid of 100mL 1mol/L, wiring solution-forming B, now in two solution, the mol ratio of ferric trichloride and aniline monomer is 1: 2;
(2) 0.01mol lithium titanate powder is added solution B, now in solution B, lithium titanate is 1: 4 with pyrroles's amount of substance ratio, again solution A is slowly added in solution B, control rate of addition, and constantly stir under 40kHz ultrasound environments, constant temperature 50 DEG C reaction 6h, product is filtered, and with deionized water and ethanol cyclic washing product, until filtrate is colourless, by the product forced air drying after washing, obtain polymer composite titanic acid lithium material.
Adopt four probe method polymer composite lithium titanate electrode of the present invention to be carried out to the test of conductivity, can obtain, the conductivity of polymer composite lithium titanate electrode of the present invention is by 10 of lithium titanate
-9s/cm magnitude brings up to 10
-1more than S/cm, substantially improves the high current charge-discharge electrical property of lithium titanate.
As can be seen from above-mentioned all embodiments, as long as use raw material listed in claim, and ensure that in preparation process, various parameter, in the scope listed by claim, can produce effective electrode material finished product.In concrete implementation process, those skilled in the art can both carry out concrete enforcement according to the prescribed limit of each technological parameter, is not limited with the above-described embodiment given by the present invention.
By above-mentioned specific embodiment to invention has been detailed description, those skilled in the art are to be understood that, in the scope not exceeding spirit of the present invention and essence, the certain amendment make the present invention and distortion, still can realize result of the present invention.
Claims (27)
1. a preparation method for polymer composite lithium titanate electrode, is characterized in that, said method comprising the steps of:
(1) oxidizing agent solution A is prepared, the protonic acid solution B of preparation conducting polymer monomer;
(2) lithium titanate powder is added in solution B, then solution A is progressively added drop-wise in solution B, under ultrasound condition, carry out mechanical agitation, react, obtain product;
(3) by above-mentioned product washing, drying, polymer composite lithium titanate electrode is obtained;
Wherein, described lithium titanate is 1:1 ~ 10 with the ratio of the amount of substance of conducting polymer monomer, and described oxidant is 1:0.25 ~ 2 with the ratio of the amount of substance of conducting polymer monomer, and the temperature of described reaction is 40 ~ 120 DEG C, and the time of described reaction is 1 ~ 30h; The concentration of the protonic acid solution of described conductive polymer monomer is 3 ~ 5mol/L; Described ultrasonic frequency is 20 ~ 50kHz; The conductivity of described polymer composite lithium titanate electrode is 10
-1more than S/cm.
2. the method for claim 1, is characterized in that, described oxidant is selected from the combination of a kind of in potassium peroxydisulfate, ammonium persulfate, ferric trichloride, hydrogen peroxide or at least two kinds.
3. the method for claim 1, is characterized in that, described conducting polymer monomer is selected from the combination of a kind of in aniline, pyrroles, thiophene, acetylene or at least two kinds.
4. method as claimed in claim 3, is characterized in that, described conducting polymer monomer is selected from the combination of a kind of in aniline, pyrroles, thiophene or at least two kinds.
5. the method for claim 1, is characterized in that, described Bronsted acid is selected from the combination of a kind of in hydrochloric acid, sulfuric acid, nitric acid or at least two kinds.
6. the method for claim 1, is characterized in that, the concentration of the protonic acid solution of described conductive polymer monomer is 3 ~ 4mol/L.
7. method as claimed in claim 6, it is characterized in that, the concentration of the protonic acid solution of described conductive polymer monomer is 3mol/L.
8. the method as described in one of claim 1-3, is characterized in that, described lithium titanate is 1:3 ~ 8 with the ratio of the amount of substance of conducting polymer monomer.
9. the method as described in one of claim 1-3, is characterized in that, described lithium titanate is 1:4 with the ratio of the amount of substance of conducting polymer monomer.
10. the method as described in one of claim 1-3, is characterized in that, described oxidant is 1:1 ~ 2 with the ratio of the amount of substance of conducting polymer monomer.
11. methods as claimed in claim 10, it is characterized in that, described oxidant is 1:2 with the ratio of the amount of substance of conducting polymer monomer.
12. the method for claim 1, is characterized in that, described ultrasonic frequency is 40kHz.
13. methods as described in one of claim 1-3, it is characterized in that, the temperature of described reaction is 40 ~ 100 DEG C.
14. methods as claimed in claim 13, is characterized in that, the temperature of described reaction is 40 ~ 80 DEG C.
15. methods as described in one of claim 1-3, it is characterized in that, the time of described reaction is 1.5 ~ 28h.
16. methods as claimed in claim 15, is characterized in that, the time of described reaction is 2 ~ 24h.
17. methods as described in one of claim 1-3, is characterized in that, described washing adopts water and organic solvent to carry out.
18. methods as claimed in claim 17, it is characterized in that, described water is deionized water.
19. methods as claimed in claim 18, is characterized in that, described organic solvent is selected from the combination of a kind of in acetone, ethanol, ether or at least two kinds.
20. methods as described in one of claim 1-3, is characterized in that, described drying is selected from the combination of a kind of in forced air drying, vacuumize, microwave drying, infrared drying or at least two kinds.
21. methods as claimed in claim 20, it is characterized in that, described drying is selected from vacuumize.
22. methods as claimed in claim 20, it is characterized in that, described vacuum drying temperature is 35 ~ 150 DEG C.
23. methods as claimed in claim 22, it is characterized in that, described vacuum drying temperature is 40 ~ 130 DEG C.
24. methods as claimed in claim 23, it is characterized in that, described vacuum drying temperature is 40 ~ 120 DEG C.
25. methods as claimed in claim 20, it is characterized in that, the described vacuum drying time is 18 ~ 30h.
26. methods as claimed in claim 25, it is characterized in that, the described vacuum drying time is 20 ~ 26h.
27. methods as claimed in claim 26, it is characterized in that, the described vacuum drying time is 24h.
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| CN201210018023.6A CN102569767B (en) | 2012-01-19 | 2012-01-19 | Polymer composite lithium titanate electrode material and preparation method thereof |
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| CN108232122A (en) * | 2018-01-22 | 2018-06-29 | 南京大学射阳高新技术研究院 | The preparation method and application of the lithium titanate nano particle of PEDOT claddings |
| CN109037604A (en) * | 2018-06-13 | 2018-12-18 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of polyaniline-coated lithium titanate anode material |
| CN109119622A (en) * | 2018-09-25 | 2019-01-01 | 上海电气集团股份有限公司 | Lithium-titanium composite oxide, modified lithium titanate material and preparation method thereof, application |
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| CN1492523A (en) * | 2002-09-23 | 2004-04-28 | 三星Sdi株式会社 | Lithium cell negative pole and lithium cell containing it |
| CN101237036B (en) * | 2008-01-21 | 2010-06-02 | 湘潭大学 | Making method for positive material LiFePO4 of poly-aniline coated lithium ion battery |
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