CN104577090A - Method for preparing carbon and oxide composite modified lithium titanate material - Google Patents
Method for preparing carbon and oxide composite modified lithium titanate material Download PDFInfo
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- CN104577090A CN104577090A CN201410808197.1A CN201410808197A CN104577090A CN 104577090 A CN104577090 A CN 104577090A CN 201410808197 A CN201410808197 A CN 201410808197A CN 104577090 A CN104577090 A CN 104577090A
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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
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- 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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a method for preparing a carbon and oxide composite modified lithium titanate material. The method is characterized by comprising the following steps: (1) weighing a lithium salt and nanometer titania according to a molar ratio of Li to Ti being 0.82-1, adding a dispersing agent, magnetically stirring, compounding and drying the obtained slurry by utilizing microwaves, adding the dried precursor in a muffle furnace under an air atmosphere, and naturally cooling to room temperature, thereby obtaining a nanometer lithium titanate material; (2) preparing a metal salt solution, adding ammonia water to regulate the pH value, weighing the nanometer lithium titanate material according to the ratio, stirring and standing in the metal salt solution, filtering, washing and drying, thereby obtaining a metal hydroxide coated nanometer lithium titanate material; and (3) respectively weighing a carbon source, the metal hydroxide coated nanometer lithium titanate material and deionized water, performing ball milling in a ball-milling jar, and naturally cooling to room temperature, thereby obtaining the carbon and oxide composite modified lithium titanate material.
Description
Technical field
The present invention relates to the preparation of a kind of electrochemical material, particularly relate to the preparation method of a kind of carbon and the composite modified lithium titanate material of oxide.
Background technology
Society, lithium ion battery has become one of the study hotspot in novel secondary chemical cell power sources field, and compared to conventional batteries, it has, and average discharge volt is high, volume and capacity ratio large, the advantage of good cycle.The quality of performance of lithium-ion secondary battery depends on its anode and cathode active materials.
Spinel type lithium titanate has obvious advantage as lithium ion battery negative material compared to other carbon negative pole materials: it has higher Ti
4+/ Ti
3+(1.55V vs Li
+/ Li) redox potential, electrode does not react with common electrolyte solution in the course of the work, has higher energy conversion efficiency, has higher fail safe than Carbon anode and lithium metal; Lithium ion embeds wherein and deviates from process in which materials structure and changes hardly, has more excellent cycle performance and life-span than Carbon anode, it is called as " zero strain " electrode material; It has desirable charge and discharge platform, and platform capacity can reach more than 90% of discharge capacity, has obvious voltage jump feature after discharge and recharge terminates, and does not need to add anti-overcharge device; It has higher electrochemical diffusion coefficient, is conducive to the quick deintercalation reaction of lithium ion, is applicable to fast charging and discharging.As can be seen here, lithium titanate material is the negative material that lithium ion battery has development prospect, has huge researching value and commercial value.
Conventional pure phase lithium titanate material conductivity is on the low side, high-multiplying power discharge capacity attenuation is very fast, the tap density density of material is lower, these all limit widely using of lithium titanate anode material, therefore need to carry out study on the modification to pure phase lithium titanate, thus realize its high rate capability, mainly at present to set about from two aspects: one is the nano barium titanate lithium material preparing uniform particle sizes distribution; Two is the electronics and the ionic conducting property that improve this material.
Patent CN 102376947A discloses a kind of preparation method of aluminum-oxide-coated nano lithium titanate composite material.First they prepare pure phase nanometer lithium titanate material, then nano barium titanate lithium material is carried out the suspension that dispersion treatment prepares lithium titanate, aluminum salt solution is added in the most backward lithium titanate suspension, filtration after adjust ph stirring reaction leaves standstill, washing, drying, finally sintering obtains aluminum-oxide-coated nano lithium titanate composite material.Patent CN 102001701A discloses a kind of preparation method of carbon-coated nano lithium titanate material.First they utilize chemical vapour deposition technique at TiO
2the coated with conductive carbon-coating of presoma surface uniform, and then by carbon-coated nano TiO
2with lithium salts according to necessarily measuring than mixing, sintering under inert gas atmosphere and obtaining carbon-coated nano lithium titanate material, after lower 10 circulations of 1C, specific capacity is that after lower 10 circulations of about 165mAh/g, 5C, specific capacity is about 155mAh/g.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of carbon and the composite modified lithium titanate material of oxide, for the problem of the material high rate performance difference that the electronic conductivity difference band of pure phase lithium titanate material comes, carbon and metal oxide coating modification are carried out to lithium titanate material, thus improve the conductance of lithium titanate, realize the high rate capability of material and the raising of cycle performance.
For achieving the above object, the technical solution used in the present invention is:
The preparation method of a kind of carbon and the composite modified lithium titanate material of oxide, it is characterized in that: step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add dispersant, magnetic agitation 2 ~ 5 hours, the slurry obtained utilizes microwave chemical combination drying 10 ~ 30 minutes, 600 ~ 700 DEG C of pre-burnings 2 ~ 5 hours are first risen to the heating rate of 1 ~ 10 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, 750 ~ 900 DEG C of insulations 10 ~ 16 hours are risen to again with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material,
(2) preparation of the coated lithium titanate material of metal hydroxides: preparing metal salting liquid, adding ammoniacal liquor adjust ph is 4.0 ~ 6.5, taking nano barium titanate lithium material according to proportioning adds in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take carbon source and the coated nano lithium titanate of metal hydroxides and deionized water ball milling 2 hours in ball grinder respectively, the slurry obtained utilizes microwave chemical combination drying 10 ~ 30 minutes, dried material is risen to 600 ~ 800 DEG C of sintering after 5 ~ 12 hours with the heating rate of 1 ~ 10 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
In the method, described lithium salts is the one in lithium acetate, lithium oxalate, lithium carbonate, lithium hydroxide, lithium nitrate or lithium fluoride, described nano titanium oxide is anatase structured nano titanium oxide, and described dispersant is one or more mixing in absolute ethyl alcohol, deionized water or acetone.
In the method, described slaine is Al (NO
3)
3, MgSO
4, Ni (NO
3)
2or Co (NO
3)
2in one; The concentration of the metal salt solution of preparation is 0.05 ~ 0.15mol/L; The quality of the nano barium titanate lithium material taken is counted according to the quality of metal oxide coated in theory, makes metal oxide be 1.0 ~ 4.0% relative to the mass fraction of lithium titanate.
In the method, the amount of the described carbon source taken is 5.0 ~ 16.0% relative to the mass fraction of lithium titanate.
In the method, described carbon source is the one in glucose, sucrose, starch or citric acid.
In the method, step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, 600 DEG C of pre-burnings 4 hours are first risen to the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, rise to 750 DEG C of insulations 13 hours with identical speed again, naturally cool to room temperature and namely obtain nano barium titanate lithium material;
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 1.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 6.0% relative to the mass fraction of lithium titanate, add deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
In the method, step is as follows:
(1) preparation of nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, first rise to 600 DEG C of pre-burnings 4 hours with the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, then rise to 750 DEG C of insulations 13 hours with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material;
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution of preparation 0.1mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 2.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 9.0% relative to the mass fraction of lithium titanate, add deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
In the method, step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, 600 DEG C of pre-burnings 4 hours are first risen to the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, rise to 750 DEG C of insulations 13 hours with identical speed again, naturally cool to room temperature and namely obtain nano barium titanate lithium material.
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 3.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process.
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is relative to the mass fraction 12.0% of lithium titanate, add deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
In the method, step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, 600 DEG C of pre-burnings 4 hours are first risen to the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, rise to 750 DEG C of insulations 13 hours with identical speed again, naturally cool to room temperature and namely obtain nano barium titanate lithium material.
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 4.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 16.0% relative to the mass fraction of lithium titanate, the deionized water added again ball milling 2 hours in ball grinder, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
Advantageous effect of the present invention is: owing to using this method of the present invention, this preparation method's technological process is simple, be easy to realize suitability for industrialized production, the lithium titanate composite material of preparation has excellent chemical property, lithium titanate composite material prepared by the present invention overcomes the problem of pure phase lithium titanate material electron conduction rate variance, and cycle performance and high rate performance obtain effective raising.
Accompanying drawing explanation
Fig. 1 is (0.2C) first charging and discharging curve of lithium titanate composite material, and voltage range is 0.8 ~ 2.0V;
Fig. 2 is the cycle performance resolution chart of lithium titanate composite material under 1C multiplying power.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described:
The present invention is as Fig. 1, shown in 2, the preparation method of a kind of carbon and the composite modified lithium titanate material of oxide, it is characterized in that: step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add dispersant, magnetic agitation 2 ~ 5 hours, the slurry obtained utilizes microwave chemical combination drying 10 ~ 30 minutes, 600 ~ 700 DEG C of pre-burnings 2 ~ 5 hours are first risen to the heating rate of 1 ~ 10 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, 750 ~ 900 DEG C of insulations 10 ~ 16 hours are risen to again with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material, (2) preparation of the coated lithium titanate material of metal hydroxides: preparing metal salting liquid, adding ammoniacal liquor adjust ph is 4.0 ~ 6.5, taking nano barium titanate lithium material according to proportioning adds in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process, (3) preparation of carbon and the composite modified lithium titanate material of oxide: take carbon source and the coated nano lithium titanate of metal hydroxides and deionized water ball milling 2 hours in ball grinder respectively, the slurry obtained utilizes microwave chemical combination drying 10 ~ 30 minutes, dried material is risen to 600 ~ 800 DEG C of sintering after 5 ~ 12 hours with the heating rate of 1 ~ 10 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
In the present embodiment, described lithium salts is the one in lithium acetate, lithium oxalate, lithium carbonate, lithium hydroxide, lithium nitrate or lithium fluoride, described nano titanium oxide is anatase structured nano titanium oxide, and described dispersant is one or more mixing in absolute ethyl alcohol, deionized water or acetone.
In the present embodiment, described slaine is Al (NO
3)
3, MgSO
4, Ni (NO
3)
2or Co (NO
3)
2in one; The concentration of the metal salt solution of preparation is 0.05 ~ 0.15mol/L; The quality of the nano barium titanate lithium material taken is counted according to the quality of metal oxide coated in theory, makes metal oxide be 1.0 ~ 4.0% relative to the mass fraction of lithium titanate.
In the present embodiment, the amount of the described carbon source taken is 5.0 ~ 16.0% relative to the mass fraction of lithium titanate.
In the present embodiment, described carbon source is the one in glucose, sucrose, starch or citric acid.
Embodiment 1
(1) preparation of nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, first rise to 600 DEG C of pre-burnings 4 hours with the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, then rise to 750 DEG C of insulations 13 hours with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material.
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding proper ammonia adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 1.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process.
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 6.0% relative to the mass fraction of lithium titanate, add appropriate deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
Embodiment 2
(1) preparation of nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, first rise to 600 DEG C of pre-burnings 4 hours with the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, then rise to 750 DEG C of insulations 13 hours with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material.
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding proper ammonia adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 2.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process.
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 9.0% relative to the mass fraction of lithium titanate, add appropriate deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
Embodiment 3
(1) preparation of nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, first rise to 600 DEG C of pre-burnings 4 hours with the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, then rise to 750 DEG C of insulations 13 hours with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material.
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding proper ammonia adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 3.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process.
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 12.0% relative to the mass fraction of lithium titanate, add appropriate deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
Embodiment 4
(1) preparation of nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, first rise to 600 DEG C of pre-burnings 4 hours with the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, then rise to 750 DEG C of insulations 13 hours with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material.
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding proper ammonia adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 4.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process.
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 16.0% relative to the mass fraction of lithium titanate, add appropriate deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
Embodiment result shows, when the covering amount of metal oxide is 3.0%, the chemical property of the lithium titanate composite material prepared when the covering amount of carbon source is 9.0% is best, is the negative material that lithium ion battery is good.In above-described embodiment, carbon source only lists the situation of glucose, select other carbon sources as sucrose, starch, citric acid and glucose the experimental result that produces similar.
The lithium titanate composite material of gained in above-described embodiment is assembled into mould battery, and in mould battery, material proportion is Li
4ti
5o
12: SP:PVDF=90:5:5, adopt Clgard2300 type barrier film, negative pole is lithium sheet, carries out charge-discharge performance test respectively with 0.2C, 0.5C, 1.0C multiplying power, and charging/discharging voltage is 0.8 ~ 2.0V.Fig. 1 gives the first charge-discharge curve of prepared lithium titanate composite material under 0.2C multiplying power, its under 1C multiplying power cycle performance test as shown in Figure 2.As seen from the figure, the lithium titanate composite material high rate performance prepared of the method and cycle performance all better.
Embodiment recited above is only be described the preferred embodiment of the present invention; not design of the present invention and protection range are limited; under the prerequisite not departing from design concept of the present invention; the various modification that in this area, common engineers and technicians make technical scheme of the present invention and improvement, all should fall into protection scope of the present invention.
Claims (9)
1. the preparation method of a carbon and the composite modified lithium titanate material of oxide, it is characterized in that: step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add dispersant, magnetic agitation 2 ~ 5 hours, the slurry obtained utilizes microwave chemical combination drying 10 ~ 30 minutes, 600 ~ 700 DEG C of pre-burnings 2 ~ 5 hours are first risen to the heating rate of 1 ~ 10 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, 750 ~ 900 DEG C of insulations 10 ~ 16 hours are risen to again with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material,
(2) preparation of the coated lithium titanate material of metal hydroxides: preparing metal salting liquid, adding ammoniacal liquor adjust ph is 4.0 ~ 6.5, taking nano barium titanate lithium material according to proportioning adds in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take carbon source and the coated nano lithium titanate of metal hydroxides and deionized water ball milling 2 hours in ball grinder respectively, the slurry obtained utilizes microwave chemical combination drying 10 ~ 30 minutes, dried material is risen to 600 ~ 800 DEG C of sintering after 5 ~ 12 hours with the heating rate of 1 ~ 10 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
2. the preparation method of a kind of carbon according to claim 1 and the composite modified lithium titanate material of oxide, it is characterized in that: described lithium salts is the one in lithium acetate, lithium oxalate, lithium carbonate, lithium hydroxide, lithium nitrate or lithium fluoride, described nano titanium oxide is anatase structured nano titanium oxide, and described dispersant is one or more mixing in absolute ethyl alcohol, deionized water or acetone.
3. the preparation method of a kind of carbon according to claim 1 and 2 and the composite modified lithium titanate material of oxide, is characterized in that: described slaine is Al (NO
3)
3, MgSO
4, Ni (NO
3)
2or Co (NO
3)
2in one; The concentration of the metal salt solution of preparation is 0.05 ~ 0.15mol/L; The quality of the nano barium titanate lithium material taken is counted according to the quality of metal oxide coated in theory, makes metal oxide be 1.0 ~ 4.0% relative to the mass fraction of lithium titanate.
4. the preparation method of a kind of carbon according to claim 3 and the composite modified lithium titanate material of oxide, is characterized in that: the amount of the described carbon source taken is 5.0 ~ 16.0% relative to the mass fraction of lithium titanate.
5. the preparation method of a kind of carbon according to claim 4 and the composite modified lithium titanate material of oxide, is characterized in that: described carbon source is the one in glucose, sucrose, starch or citric acid.
6. the preparation method of a kind of carbon according to claim 1 and the composite modified lithium titanate material of oxide, it is characterized in that: step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, 600 DEG C of pre-burnings 4 hours are first risen to the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, 750 DEG C of insulations 13 hours are risen to again with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material,
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 1.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 6.0% relative to the mass fraction of lithium titanate, add deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
7. the preparation method of a kind of carbon according to claim 1 and the composite modified lithium titanate material of oxide, is characterized in that: step is as follows:
(1) preparation of nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, first rise to 600 DEG C of pre-burnings 4 hours with the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, then rise to 750 DEG C of insulations 13 hours with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material;
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution of preparation 0.1mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 2.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 9.0% relative to the mass fraction of lithium titanate, add deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
8. the preparation method of a kind of carbon according to claim 1 and the composite modified lithium titanate material of oxide, it is characterized in that: step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, 600 DEG C of pre-burnings 4 hours are first risen to the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, 750 DEG C of insulations 13 hours are risen to again with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material,
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 3.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is relative to the mass fraction 12.0% of lithium titanate, add deionized water ball milling 2 hours in ball grinder again, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
9. the preparation method of a kind of carbon according to claim 1 and the composite modified lithium titanate material of oxide, it is characterized in that: step is as follows: the preparation of (1) nano barium titanate lithium material: the proportioning being Li:Ti=0.82:1 according to mol ratio takes lithium salts and nano titanium oxide, the two is mixed, add deionized water, magnetic agitation 2 hours, the slurry obtained utilizes microwave chemical combination dry 30 minutes, 600 DEG C of pre-burnings 4 hours are first risen to the heating rate of 5 DEG C/min under dried presoma being placed in Muffle furnace air atmosphere, 750 DEG C of insulations 13 hours are risen to again with identical speed, naturally cool to room temperature and namely obtain nano barium titanate lithium material,
(2) preparation of the coated lithium titanate material of metal hydroxides: the metal salt solution preparing 0.1 mol/L, adding ammoniacal liquor adjust ph is 6.0, take make the theoretical covering amount of metal oxide be 4.0% nano barium titanate lithium material add in metal salt solution, stirring reaction is after 2 hours, leave standstill 14 hours, after filtration, washing, obtain the coated nano barium titanate lithium material of metal hydroxides after dry process;
(3) preparation of carbon and the composite modified lithium titanate material of oxide: take glucose and the coated nano lithium titanate of metal hydroxides respectively, wherein the amount of glucose is 16.0% relative to the mass fraction of lithium titanate, the deionized water added again ball milling 2 hours in ball grinder, the slurry obtained utilizes microwave chemical combination dry 30 minutes, dried material is risen to 650 DEG C of sintering after 5 hours with the heating rate of 5 DEG C/min in a nitrogen atmosphere, naturally cools to room temperature and namely obtain carbon and the composite modified lithium titanate material of oxide.
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