CN101924201A - Method for preparing lithium ion battery negative material carbon-coated and metal-doped lithium titanate - Google Patents
Method for preparing lithium ion battery negative material carbon-coated and metal-doped lithium titanate Download PDFInfo
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Abstract
The invention discloses a method for preparing lithium ion battery negative material carbon-coated and metal-doped lithium titanate (Li4Ti5O12). In the method, a lithium source compound and metatitanic acid serve as raw materials, or the lithium source compound, the metatitanic acid and a metal source compound serve as the raw materials. The method comprises the following steps of: adding the raw materials into a planetary ball mill to perform ball milling and mixing; mixing the raw materials uniformly to obtain a precursor; drying and pulverizing the precursor to obtain fine powder; and placing the fine powder into a crucible to perform heat treatment for 25 to 45 minutes at the temperature of between 650 and 850 DEG C by using microwaves under a non-oxidation atmosphere to obtain the lithium ion battery negative material carbon-coated and metal-doped lithium titanate. The method for preparing the lithium ion battery negative material carbon-coated and metal-doped lithium titanate has the advantages of simple production process, low cost and energy consumption, high yield and easy industrial implementation. The product prepared by the technical scheme of the invention has the advantages of high electrical conductivity, lower resistance and polarization, high energy density of the batter and capacities of greatly improving the electrical conductivity of the Li4Ti5O12 and effectively increasing the charge-discharge capacity and cycle index.
Description
One, technical field:
The present invention relates to a kind of preparation method of lithium ion battery negative pole active materials, particularly relate to the preparation method of a kind of lithium ion battery negative material carbon coating and metal-doped lithium titanate.
Two, background technology:
Lithium ion battery will be with a wide range of applications in fields such as electric automobile, satellite, space flight and military affairs as energy and material of new generation.Wherein negative material is the important component part of lithium ion battery, researches and develops the key point that high performance negative material has become the lithium ion battery development.
Carbonaceous material is research of people's early start and the material that is applied to lithium ion battery negative.Carbonaceous material mainly has the following advantages: the specific capacity height, electrode potential is low, cycle efficieny is high, have extended cycle life.At present, commercial lithium ion battery negative material adopts embedding lithium material with carbon element mostly.Although for lithium metal, material with carbon element has had very big improvement at aspects such as security performance, cycle performances, still have many shortcomings: 1, when discharging and recharging for the first time, can form passivating film (SEI film) at carbon surface, cause capacitance loss; 2, the current potential of the current potential of carbon electrode and lithium is very approaching, and when battery overcharge, lithium metal may be separated out in carbon electrodes, forms dendrite and causes safety issue.
And spinel lithium titanate (Li
4Ti
5O
12) be the insertion material of a kind of " zero strain ", Stability Analysis of Structures, good cycle, and its removal lithium embedded current potential is higher than the reduction potential of most of electrolyte, thereby it is as the negative material of lithium ion battery, has higher fail safe.From the angle of structure, Li
4Ti
5O
12Be desirable embedded type electrode, the growth of its cell volume parameter in charge and discharge process can be ignored, and electrode structure can hold a large amount of lithium ions.By the degree of depth that restriction discharges and recharges, can keep the integrality of electrode structure, and can obtain bigger cycle life.But Li
4Ti
5O
12Have relatively poor electron conduction and relative higher voltage platform, this has just limited its high rate capability.Discover, by other ion that mixes, at Li
4Ti
5O
12In cause certain Ti
4+/ Ti
3+Be to improve Li
4Ti
5O
12An effective way of material electronics conductivity.
Report about the lithium ionic cell cathode material lithium titanate pertinent literature also has much.For example: 1, application number is that 200910145062.0 patent of invention discloses a kind of lithium ionic cell cathode material lithium titanate and preparation method thereof.2, application number is the preparation method that 200810203991.8 patent of invention discloses a kind of lithium ionic cell cathode material lithium titanate.3, application number is the preparation method that 200810204016.9 patent of invention discloses a kind of lithium ionic cell cathode material lithium titanate.
Three, content of the present invention:
The technical problem to be solved in the present invention is: overcome the shortcoming that the specific capacity of lithium ionic cell cathode material lithium titanate is relatively low in the prior art, electric conductivity is relatively poor, cost is high, the lithium ion battery negative material carbon coating of a kind of negative material charge/discharge capacity height that the cost of material is low, energy consumption is low and make, good cycle and the preparation method of metal-doped lithium titanate are provided.
In order to address the above problem, the technical solution used in the present invention is:
The invention provides the preparation method that a kind of lithium ion battery negative material carbon coats lithium titanate, described preparation method may further comprise the steps:
A, according to Li source compound and metatitanic acid between the two mol ratio be 1: 0.8～0.9 proportioning ratio, take by weighing Li source compound and metatitanic acid, add carbon or the carbon compound that accounts for two kinds of raw material total weight 5～30wt% then, obtain presoma after evenly mixing;
B, the precursor that step a is obtained are put into baking oven and carried out drying, and be dry after pulverize and obtain fine powder;
C, the fine powder that step b is obtained place alumina crucible or graphite crucible, are utilizing microwave heat treatment 25～45 minutes under 650～850 ℃ of temperature under the non-oxide atmosphere condition, prepare lithium ion battery negative material carbon after microwave thermal is handled and coat lithium titanate.
According to the preparation method of above-mentioned lithium ion battery negative material carbon coating lithium titanate, Li source compound described in the step a is lithium hydroxide, lithium acetate or lithium nitrate; Described carbon or carbon compound be in graphite, acetylene black, polyvinyl alcohol, polyethylene glycol, the dextrose plus saccharose any or appoint several.
Coat the preparation method of lithium titanate according to above-mentioned lithium ion battery negative material carbon, the even mixing of raw material described in the step a is that various raw materials are mixed in planetary ball mill, add the dispersant acetone or alcohol when in ball mill, mixing, the addition of dispersant accounts for 100～200wt% of Li source compound, metatitanic acid and carbon or three kinds of raw material total amounts of carbon compound, described when in planetary ball mill, mixing earlier with 400 rev/mins of ball millings 5～10 minutes, and then with 200 rev/mins of ball millings 30～60 minutes.
According to the preparation method of above-mentioned lithium ion battery negative material carbon coating lithium titanate, baking temperature is 90～120 ℃ when carrying out drying described in the step b, and be 3～6 hours drying time; The granularity of fine powder was 200 mesh sieves among the step b.
According to the preparation method of above-mentioned lithium ion battery negative material carbon coating lithium titanate, non-oxide atmosphere described in the step c is meant in atmosphere of inert gases or under vacuum condition; Described inert gas is meant nitrogen, argon gas or helium, and the vacuum degree of described vacuum condition is less than 10 handkerchiefs; The power of described microwave oven is 5～15kw.
A kind of preparation method of lithium ion battery negative material metal-doped lithium titanate, described preparation method may further comprise the steps:
A, according to the mol ratio between Li source compound, metatitanic acid and the metal source compound three 1: 0.8～0.9: 0.01～0.05 ratio, take by weighing Li source compound, metatitanic acid and metal source compound respectively, obtain presoma after its three kinds of raw materials are evenly mixed;
B, the presoma that step a is obtained are put into baking oven and carried out drying, and be dry after pulverize and obtain fine powder;
C, the fine powder that step b is obtained place alumina crucible or graphite crucible, are utilizing microwave heat treatment 25～45 minutes under 650～850 ℃ of temperature under the non-oxide atmosphere, and microwave thermal is prepared the lithium ion battery negative material metal-doped lithium titanate after handling.
According to the preparation method of above-mentioned lithium ion battery negative material metal-doped lithium titanate, Li source compound described in the step a is lithium hydroxide, lithium carbonate or lithium nitrate; Described metal source compound is any in aluminum nitrate, chromic nitrate, chromium sulfate, ferric nitrate, ferrous sulfate, cobalt nitrate, cobaltous sulfate and the cobalt acetate.
Preparation method according to above-mentioned lithium ion battery negative material metal-doped lithium titanate, the even mixing of raw material described in the step a is that various raw materials are mixed in planetary ball mill, add the dispersant acetone or alcohol when in ball mill, mixing, the addition of dispersant accounts for 100～200% of Li source compound, metatitanic acid and carbon or three kinds of raw material total amounts of carbon compound, described when in planetary ball mill, mixing earlier with 400 rev/mins of ball millings 5～10 minutes, and then with 200 rev/mins of ball millings 30～50 minutes.
According to the preparation method of above-mentioned lithium ion battery negative material metal-doped lithium titanate, baking temperature is 90～120 ℃ when carrying out drying described in the step b, and be 3～6 hours drying time; The granularity of fine powder was 200 mesh sieves among the step b.
According to the preparation method of above-mentioned lithium ion battery negative material metal-doped lithium titanate, non-oxide atmosphere described in the step c is meant in atmosphere of inert gases or under vacuum condition; Described inert gas is meant nitrogen, argon gas or helium, and the vacuum degree of described vacuum condition is less than 10 handkerchiefs; The power of described microwave oven is 5～15kw.
Positive beneficial effect of the present invention:
1, the cheap metatitanic acid of technical solution of the present invention employing is a titanium source raw material, utilizes microwave to heat-treat and prepares lithium titanate (Li
4Ti
5O
12).Utilize Microwave Treatment that material and microwave field are interacted, microwave is by absorbed and be converted into heat energy, from material internal its integral body is heated, realization is rapidly heated, shorten the processing time greatly, improved output, reduced material cost and energy consumption, simplified technology, be easy in industrial enforcement.
2, technical solution of the present invention adopt to be mixed and to be obtained presoma, and the industrial microwave oven of utilizing high power handles that (microwave power is 5～15kw), thereby has improved the uniformity and the electric conductivity of material greatly then; Utilize Microwave Treatment technology quick heating, homogeneous heating simultaneously, prevent the advantage of reuniting, make the lithium titanate Li of its preparation
4Ti
5O
12Purity height, crystal property are good, crystal grain is tiny has evenly shortened the processing time, the sample grain refinement of processing, even structure, and the control of microwave heating is simultaneously accurately shortened generated time, and energy savings has improved labor productivity, has reduced cost.
3, the present invention is by carbon coated or carry out metal-doped to lithium titanate Li
4Ti
5O
12Carry out modification, thereby improved the conductivity of material, reduced resistance and polarization, can also reduce its electrode potential in addition, improve the energy density of battery, improving Li significantly
4Ti
5O
12In the time of conductivity, charge/discharge capacity and cycle-index have been improved effectively.
Product of the present invention at room temperature discharges and recharges with 20mA/g, not doped samples first discharge capacity be 140mAh/g, 30 times circulation back specific capacity still has 131.7mAh/g; The discharge capacity first of mixing the Al sample is 155mAh/g, and 30 times circulation back specific capacity still has 143.2mAh/g; The discharge capacity first of mixing the C sample is 166mAh/g, and 30 times circulation back specific capacity still has 153.8mAh/g.
4, accompanying drawing 1 is warming up to the XRD figure spectrum that 800 ℃ of microwave thermal are handled the not doped lithium titanate product of insulation 40min preparation for utilizing technical solution of the present invention under the argon gas atmosphere protection.
Shown by all diffraction maximums in the accompanying drawing 1: the crystal formation of sintetics is face-centred cubic structure (space group Fd3m), with the lithium titanate (Li of standard
4Ti
5O
12) diffracting spectrum compares, basically identical illustrates that the not doping product that utilizes microwave thermal Processing of Preparation of the present invention is lithium titanate, the crystal face at three strong peaks is followed successively by (111), (113) and (022) among the figure, and is corresponding one by one with the characteristic peak of standard lithium titanate.Therefore, utilize technical solution of the present invention, under the situation of any ion that undopes, the not doping product of preparing is a lithium titanate.
5, compare with the product lithium titanate of conventional heat treatment preparation, the not doping product lithium titanate that utilizes microwave thermal Processing of Preparation of the present invention to go out, its purity is higher, does not have the stray crystal phase, and product particle thinner (can be illustrated by accompanying drawing 2).
Accompanying drawing 2 is the XRD figure spectrum of the product lithium titanate of conventional heat treatment and two kinds of technical schemes preparations of microwave thermal of the present invention processing: as can be seen from Figure 2, and the principal crystalline phase Li that the sample of two kinds of heat treatment mode preparations occurs
4Ti
5O
12Closely similar, but the collection of illustrative plates that conventional method heat treatment obtains sample in 2 θ=27.48 °, 54.37 ° locate to have occurred micro-rutile, and the existence of rutile can influence negative material lithium titanate Li
4Ti
5O
12Chemical property; Microwave thermal of the present invention is handled and then can be obtained purer lithium titanate Li
4Ti
5O
12Phase does not have the stray crystal phase, and three big diffraction maximums of principal crystalline phase are wideer slightly than conventional heat treatment synthetic sample, and the sample particle thinner (among Fig. 2, c-Microwave Treatment of the present invention, the conventional heat treatment of d-) that microwave thermal processing of the present invention is made is described.
6, utilize the lithium ion battery negative material carbon of technical solution of the present invention preparation to coat lithium titanate, wherein in the lithium titanate addition of carbon to the almost not influence (can be illustrated) of spinel structure of lithium titanate by accompanying drawing 3.
Accompanying drawing 3 is the different XRD figure spectrum (Li of carbon addition in the sample lithium carbonate
4Ti
5O
12): as can be seen from Figure 3, very pure Li has all appearred in the XRD figure of four kinds of different C additions
4Ti
5O
12Diffraction maximum, assorted peak illustrates and mixes C to Li
4Ti
5O
12Almost not influence of spinel structure.Data among Fig. 3 are C and Li
4Ti
5O
12Weight ratio between the two.
7, utilize the lithium ion battery negative material of technical solution of the present invention preparation to mix the C lithium titanate, mix the Al lithium titanate and mix C, Al lithium titanate simultaneously, the various elements that mix can both obtain purer spinel-type Li
4Ti
5O
12, (can be illustrated) by accompanying drawing 4.
Accompanying drawing 4 is the XRD figure spectrum (Li of the different element gained samples that mix
4Ti
5O
12): to Li
4Ti
5O
12Doping C (C: Li
4Ti
5O
12=1: 20, weight ratio), mix Al (Li
4Ti
4.8Al
0.2O
12), mix C (1: 20) and Al (Li simultaneously
4Al
xTi
5-xO
12, X=0.1 wherein) and the XRD figure spectrum of gained sample.As shown in Figure 4, the various elements that mix can both obtain purer spinel-type Li
4Ti
5O
12, and almost not assorted peak, illustrating mixes does not change Li
4Ti
5O
12Spinel structure (all samples all is to handle the 40min gained 800 ℃ of following microwave thermal).
Four, description of drawings:
Fig. 1 not doped samples is warming up to the XRD figure spectrum that 800 ℃ of microwave thermal are handled insulation 40min preparing product under the argon gas atmosphere protection
Fig. 2: XRD figure conventional and two kinds of different heat treatment modes of microwave products therefrom is composed
Fig. 3: the different XRD figure spectrum (Li of C addition in the sample
4Ti
5O
12)
Fig. 4: the XRD figure spectrum (Li of the different element gained samples that mix
4Ti
5O
12)
Fig. 5: the SEM figure that mixes C and A1 sample in the sample simultaneously
Fig. 6: preparation method's process flow diagram of lithium ion battery negative material carbon coating of the present invention and metal-doped lithium titanate
Five, embodiment:
Following examples only in order to further specify the present invention, do not limit content of the present invention.
Embodiment 1: a kind of lithium ion battery negative material carbon coats lithium titanate (Li
4Ti
5O
12) the preparation method
A kind of lithium ion battery negative material carbon coats lithium titanate (Li
4Ti
5O
12) the preparation method, this preparation method may further comprise the steps (referring to accompanying drawing 6):
A, in lithium hydroxide and the metatitanic acid mol ratio between the two 1: 0.9 ratio, take by weighing lithium hydroxide and metatitanic acid respectively, two kinds of raw materials are carried out batch mixing, adding the graphite that accounts for two kinds of raw material total weight 10wt% then mixes, add and account for the absolute ethyl alcohol of three kinds of raw materials (lithium hydroxide, metatitanic acid and graphite) total weight 150wt% as dispersant, in planetary ball mill with 400 rev/mins of ball millings after 10 minutes, with 200 rev/mins of ball millings 40 minutes, after mixing, ball milling obtains presoma again;
B, the presoma that step a is obtained are put into baking oven and carried out drying, and the control baking temperature is 90 ℃, and be 5 hours drying time, and be dry after pulverize, and crosses 200 mesh sieves and obtain fine powder;
C, the fine powder that step b is obtained place alumina crucible, utilize microwave heat treatment 30 minutes under 650 ℃ temperature under argon atmosphere, and microwave power 5～15KW prepares lithium ion battery negative material carbon after microwave thermal is handled and coats lithium titanate (Li
4Ti
5O
12) product; At last product is pulverized, detects, packs, put in storage and get final product according to conventional method.
Embodiment 2: substantially the same manner as Example 1, difference is:
Step a: the Li source compound of employing is a lithium acetate, lithium acetate and the metatitanic acid mol ratio between the two is 1: 0.8, add the acetylene black that accounts for two kinds of raw material total amount 5wt%, in planetary ball mill, carry out in the mechanical milling process, employing acetone is dispersant, the addition of acetone accounts for the 120wt% of lithium acetate, metatitanic acid and three kinds of raw material total amounts of acetylene black, in planetary ball mill with 400 rev/mins of ball millings after 7 minutes, again with 200 rev/mins of ball millings 50 minutes;
Step b: the control baking temperature is 100 ℃, and be 4 hours drying time;
Step c: the fine powder that step b is obtained places graphite crucible, utilizes microwave heat treatment 35 minutes under 750 ℃ temperature under nitrogen atmosphere.
Embodiment 3: substantially the same manner as Example 1, difference is:
Step a: the Li source compound of employing is a lithium nitrate, lithium nitrate and the metatitanic acid mol ratio between the two is 1: 0.85, add the glucose that accounts for two kinds of raw material total amount 25wt%, in planetary ball mill, carry out in the mechanical milling process, employing ethanol is dispersant, the addition of ethanol accounts for the 200wt% of lithium nitrate, metatitanic acid and three kinds of raw material total amounts of glucose, in planetary ball mill with 400 rev/mins of ball millings after 5 minutes, again with 200 rev/mins of ball millings 60 minutes;
Step b: the control baking temperature is 120 ℃, and be 3 hours drying time.
Step c: the fine powder that step b is obtained places alumina crucible, in vacuum degree is to utilize microwave heat treatment 25 minutes under 850 ℃ temperature under the condition of 8 handkerchiefs.
Embodiment 4: substantially the same manner as Example 1, difference is:
Step a: lithium hydroxide and the metatitanic acid mol ratio between the two is 1: 0.8, add the polyethylene glycol that accounts for two kinds of raw material total amount 30wt%, in planetary ball mill, carry out in the mechanical milling process, employing acetone is dispersant, and the addition of acetone accounts for the 200wt% of lithium hydroxide, metatitanic acid and three kinds of raw material total amounts of polyethylene glycol;
Step b: the control baking temperature is 105 ℃, and be 4 hours drying time;
Step c: the fine powder that step b is obtained places graphite crucible, in vacuum degree is to utilize microwave heat treatment 45 minutes under 600 ℃ temperature under the condition of 6 handkerchiefs.
Embodiment 5: a kind of lithium ion battery negative material metal-doped lithium titanate (Li
4Ti
5O
12) the preparation method
A kind of lithium ion battery negative material metal-doped lithium titanate (Li
4Ti
5O
12) the preparation method, this preparation method may further comprise the steps (referring to accompanying drawing 6):
A, be 1: 0.9: 0.03 ratio, take by weighing lithium carbonate, metatitanic acid and chromic nitrate respectively, raw material is carried out batch mixing, doping in the mol ratio between lithium carbonate, metatitanic acid and the chromic nitrate three; Add then account for three kinds of raw material total weights 120wt% acetone as dispersant, in planetary ball mill with 400 rev/mins of ball millings after 5 minutes, again with 200 rev/mins of ball millings 50 minutes, the presoma that obtains mixing;
B, the presoma that step a is obtained are put into baking oven and carried out drying, and the control baking temperature is 100 ℃, and be 3 hours drying time, and be dry after pulverize, and crosses 200 mesh sieves and obtain fine powder;
C, the fine powder that step b is obtained place graphite crucible, utilize microwave heat treatment 25 minutes under 750 ℃ temperature under nitrogen atmosphere, microwave power 5～15KW; Microwave thermal is prepared lithium ion battery negative material metal-doped lithium titanate (Li after handling
4Ti
5O
12).
Embodiment 6: substantially the same manner as Example 5, difference is:
Step a: the Li source compound of employing is a lithium hydroxide, metal source compound is an aluminum nitrate, mol ratio between lithium hydroxide, metatitanic acid and the aluminum nitrate three is 1: 0.8: 0.02, in planetary ball mill, carry out in the process of ball milling, adopt ethanol as dispersant, the addition of ethanol accounts for the 160wt% of lithium hydroxide, metatitanic acid and three kinds of raw material total amounts of aluminum nitrate, in planetary ball mill with 400 rev/mins of ball millings after 10 minutes, again with 200 rev/mins of ball millings 30 minutes;
Step b: the control baking temperature is 90 ℃, and be 6 hours drying time;
Step c: the fine powder that step b is obtained places alumina crucible, utilizes microwave heat treatment 35 minutes under 650 ℃ temperature under argon atmosphere.
Embodiment 7: substantially the same manner as Example 5, difference is:
Step a: the Li source compound of employing is a lithium nitrate, and metal source compound is a ferrous sulfate, and the mol ratio between lithium nitrate, metatitanic acid and the ferrous sulfate three is 1: 0.85: 0.03; In planetary ball mill, carry out in the process of ball milling, adopt ethanol as dispersant, the addition of ethanol accounts for the 180wt% of lithium nitrate, metatitanic acid and three kinds of raw material total amounts of ferrous sulfate, in planetary ball mill with 400 rev/mins of ball millings after 8 minutes, again with 200 rev/mins of ball millings 40 minutes;
Step b: the control baking temperature is 120 ℃, and be 3 hours drying time;
Step c: the fine powder that step b is obtained places alumina crucible, in vacuum degree is to utilize microwave heat treatment 25 minutes under 850 ℃ temperature under the condition of 6 handkerchiefs.
Embodiment 8: substantially the same manner as Example 5, difference is:
Step a: the Li source compound of employing is a lithium carbonate, and metal source compound is a cobalt acetate, and the mol ratio between lithium carbonate, metatitanic acid and the cobalt acetate three is 1: 0.9: 0.05;
Step b: the control baking temperature is 105 ℃, and be 4 hours drying time;
Step c: the fine powder that step b is obtained places alumina crucible, in vacuum degree is to utilize microwave heat treatment 35 minutes under 700 ℃ temperature under the condition of 4 handkerchiefs.
Embodiment 9: a kind of lithium ion battery negative material carbon, metal-doped lithium titanate (Li
4Ti
5O
12) the preparation method, this method may further comprise the steps:
A, in the mol ratio between lithium carbonate, metatitanic acid and the aluminum nitrate three 1: 0.9: 0.03 ratio, take by weighing lithium carbonate, metatitanic acid and aluminum nitrate respectively, raw material is carried out batch mixing, adding the acetylene black that accounts for three kinds of raw material total weight 15wt% then mixes, add the acetone of the 160wt% that accounts for four kinds of raw materials (being lithium carbonate, metatitanic acid, aluminum nitrate and acetylene black) total weight again as dispersant, in planetary ball mill with 400 rev/mins of ball millings after 5 minutes, with 200 rev/mins of ball millings 45 minutes, ball milling obtained presoma after evenly mixing again;
B, the presoma that step a is obtained are put into baking oven and are carried out drying, and the control baking temperature is 110 ℃, and be 3 hours drying time, pulverizes after the drying, cross 200 mesh sieves and obtain fine powder;
C, the fine powder that step b is obtained place alumina crucible, utilize microwave heat treatment 30 minutes under 700 ℃ temperature under nitrogen atmosphere, microwave power 5～15KW; Microwave thermal is prepared product lithium ion battery negative material carbon, metal-doped lithium titanate (Li after handling
4Ti
5O
12).
Embodiment 10: substantially the same manner as Example 9, difference is:
Step a: replace lithium carbonate with lithium acetate, replace aluminum nitrate with cobalt nitrate, the glucose replace ethine is black.
Claims (10)
1. a lithium ion battery negative material carbon coats the preparation method of lithium titanate, it is characterized in that described preparation method may further comprise the steps:
A, according to Li source compound and metatitanic acid between the two mol ratio be 1: 0.8～0.9 proportioning ratio, take by weighing Li source compound and metatitanic acid, add carbon or the carbon compound that accounts for two kinds of raw material total weight 5～30wt% then, obtain presoma after evenly mixing;
B, the precursor that step a is obtained are put into baking oven and carried out drying, and be dry after pulverize and obtain fine powder;
C, the fine powder that step b is obtained place alumina crucible or graphite crucible, are utilizing microwave heat treatment 25～45 minutes under 650～850 ℃ of temperature under the non-oxide atmosphere condition, prepare lithium ion battery negative material carbon after microwave thermal is handled and coat lithium titanate.
2. lithium ion battery negative material carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: Li source compound described in the step a is lithium hydroxide, lithium acetate or lithium nitrate; Described carbon or carbon compound be in graphite, acetylene black, polyvinyl alcohol, polyethylene glycol, the dextrose plus saccharose any or appoint several.
3. lithium ion battery negative material carbon according to claim 1 coats the preparation method of lithium titanate, it is characterized in that: the even mixing of raw material described in the step a is that various raw materials are mixed in planetary ball mill, add the dispersant acetone or alcohol when in ball mill, mixing, the addition of dispersant accounts for Li source compound, 100～200wt% of metatitanic acid and carbon or three kinds of raw material total amounts of carbon compound, described when in planetary ball mill, mixing earlier with 400 rev/mins of ball millings 5～10 minutes, and then with 200 rev/mins of ball millings 30～60 minutes.
4. lithium ion battery negative material carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: baking temperature is 90～120 ℃ when carrying out drying described in the step b, and be 3～6 hours drying time; The granularity of fine powder was 200 mesh sieves among the step b.
5. lithium ion battery negative material carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: non-oxide atmosphere described in the step c is meant in atmosphere of inert gases or under vacuum condition; Described inert gas is meant nitrogen, argon gas or helium, and the vacuum degree of described vacuum condition is less than 10 handkerchiefs; The power of described microwave oven is 5～15kw.
6. the preparation method of a lithium ion battery negative material metal-doped lithium titanate is characterized in that, described preparation method may further comprise the steps:
A, according to the mol ratio between Li source compound, metatitanic acid and the metal source compound three 1: 0.8～0.9: 0.01～0.05 ratio, take by weighing Li source compound, metatitanic acid and metal source compound respectively, obtain presoma after its three kinds of raw materials are evenly mixed;
B, the presoma that step a is obtained are put into baking oven and carried out drying, and be dry after pulverize and obtain fine powder;
C, the fine powder that step b is obtained place alumina crucible or graphite crucible, are utilizing microwave heat treatment 25～45 minutes under 650～850 ℃ of temperature under the non-oxide atmosphere, and microwave thermal is prepared the lithium ion battery negative material metal-doped lithium titanate after handling.
7. the preparation method of lithium ion battery negative material metal-doped lithium titanate according to claim 6 is characterized in that: Li source compound described in the step a is lithium hydroxide, lithium carbonate or lithium nitrate; Described metal source compound is any in aluminum nitrate, chromic nitrate, chromium sulfate, ferric nitrate, ferrous sulfate, cobalt nitrate, cobaltous sulfate and the cobalt acetate.
8. the preparation method of lithium ion battery negative material metal-doped lithium titanate according to claim 6, it is characterized in that: the even mixing of raw material described in the step a is that various raw materials are mixed in planetary ball mill, add the dispersant acetone or alcohol when in ball mill, mixing, the addition of dispersant accounts for Li source compound, 100～200% of metatitanic acid and carbon or three kinds of raw material total amounts of carbon compound, described when in planetary ball mill, mixing earlier with 400 rev/mins of ball millings 5～10 minutes, and then with 200 rev/mins of ball millings 30～50 minutes.
9. the preparation method of lithium ion battery negative material metal-doped lithium titanate according to claim 6 is characterized in that: baking temperature is 90～120 ℃ when carrying out drying described in the step b, and be 3～6 hours drying time; The granularity of fine powder was 200 mesh sieves among the step b.
10. the preparation method of lithium ion battery negative material metal-doped lithium titanate according to claim 6 is characterized in that: non-oxide atmosphere described in the step c is meant in atmosphere of inert gases or under vacuum condition; Described inert gas is meant nitrogen, argon gas or helium, and the vacuum degree of described vacuum condition is less than 10 handkerchiefs; The power of described microwave oven is 5～15kw.
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| CN2010102358978A CN101924201A (en) | 2010-07-26 | 2010-07-26 | Method for preparing lithium ion battery negative material carbon-coated and metal-doped lithium titanate |
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| CN102364729A (en) * | 2011-11-10 | 2012-02-29 | 中南大学 | High-power Li4Ti5O12/activated carbon composite electrode material and preparation method thereof |
| CN102569772A (en) * | 2012-03-16 | 2012-07-11 | 湖南大学 | High-coulombic-efficiency negative electrode active material of carbon-coated lithium-rich lithium titanate of lithium ion battery and preparation method for high-coulombic-efficiency negative electrode active material of carbon-coated lithium-rich lithium titanate |
| CN102983381A (en) * | 2012-11-06 | 2013-03-20 | 中国科学院大连化学物理研究所 | Energy storage device with interleaved distributed inner parallel structure |
| CN104550940A (en) * | 2013-10-29 | 2015-04-29 | 东睦新材料集团股份有限公司 | Method for coating metal magnetic powder on soft magnetic ferrites and method for preparing soft magnetic composite materials |
| CN103474645B (en) * | 2013-09-22 | 2016-01-20 | 四川科能锂电有限公司 | The preparation method of lithium titanate |
| CN105355855A (en) * | 2015-11-13 | 2016-02-24 | 山东精工电子科技有限公司 | Method for preparing high voltage cathode material LiNiVO4 by explosion method |
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| CN107732222A (en) * | 2017-11-02 | 2018-02-23 | 洛阳月星新能源科技有限公司 | A kind of lithium titanate composite material and preparation method thereof, lithium titanate battery |
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| CN102569772A (en) * | 2012-03-16 | 2012-07-11 | 湖南大学 | High-coulombic-efficiency negative electrode active material of carbon-coated lithium-rich lithium titanate of lithium ion battery and preparation method for high-coulombic-efficiency negative electrode active material of carbon-coated lithium-rich lithium titanate |
| CN102983381A (en) * | 2012-11-06 | 2013-03-20 | 中国科学院大连化学物理研究所 | Energy storage device with interleaved distributed inner parallel structure |
| CN103474645B (en) * | 2013-09-22 | 2016-01-20 | 四川科能锂电有限公司 | The preparation method of lithium titanate |
| CN104550940B (en) * | 2013-10-29 | 2016-09-21 | 东睦新材料集团股份有限公司 | The method of a kind of soft magnetic ferrite cladding metallic magnetic powder and soft-magnetic composite material preparation method thereof |
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| CN106876692A (en) * | 2017-04-07 | 2017-06-20 | 宁波大学 | A kind of lithium position silver-bearing copper chromium codope cooperates with the preparation method of nitrogen sulfur doping coated modified carbon barium titanate lithium titanate cathode material |
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| CN106848266B (en) * | 2017-04-07 | 2019-03-19 | 宁波大学 | A kind of preparation method of lithium position sodium-doped collaboration nitrogen-doped carbon coating modification barium titanate lithium titanate cathode material |
| CN107732222A (en) * | 2017-11-02 | 2018-02-23 | 洛阳月星新能源科技有限公司 | A kind of lithium titanate composite material and preparation method thereof, lithium titanate battery |
| CN107732222B (en) * | 2017-11-02 | 2020-06-26 | 洛阳月星新能源科技有限公司 | Lithium titanate composite material, preparation method thereof and lithium titanate battery |
| CN109888247A (en) * | 2019-03-25 | 2019-06-14 | 四川轻化工大学 | A kind of lithium ion battery zinc titanate lithium/carbon nano composite anode material preparation method |
| CN109888247B (en) * | 2019-03-25 | 2021-10-15 | 四川轻化工大学 | Preparation method of lithium zinc titanate/carbon nano composite negative electrode material for lithium ion battery |
| CN110323436A (en) * | 2019-07-11 | 2019-10-11 | 银隆新能源股份有限公司 | The electrode slice and preparation method thereof and lithium ion battery of lithium titanate composite material and preparation method thereof, lithium ion battery |
| CN110323436B (en) * | 2019-07-11 | 2023-04-11 | 银隆新能源股份有限公司 | Lithium titanate composite material and preparation method thereof, electrode plate of lithium ion battery and preparation method thereof, and lithium ion battery |
| CN112624183A (en) * | 2020-12-21 | 2021-04-09 | 四川大学 | Lithium titanate for preparing lithium battery negative electrode material, preparation method and application |
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