CN107749469A - The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide - Google Patents
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention belongs to the preparing technical field of lithium cell cathode material, there is provided the negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide.This method uses melamine and urea, and under the conditions of catalyst and methanol, by controlling the reaction condition in addition and each stage stage by stage of urea, the carbon nitride precursor slurry of the class graphene-structured of two dimensional surface is made.Then high temperature sintering after slurry is mixed with titanium dioxide, the negative material of carbonitride carried titanium dioxide is obtained.Compared with conventional method, nano silicon nitride carbon produced by the present invention has preferable charge-discharge performance and cycle performance, the specific capacity of battery is higher, review negative material has good modulus of elasticity and Mohs' hardness, good mechanical performance, while whole process reaction condition is gentle, it is easy to control, cost is appropriate, can reach preferable cost performance.
Description
Technical field
The invention belongs to the preparing technical field of lithium cell cathode material, there is provided a kind of lithium battery loads two with carbonitride
The negative material and preparation method of titanium oxide.
Background technology
Lithium ion battery (Li-ion Batteries) is that lithium battery develops, and is characterized in using Carbon Materials as negative pole,
Make the lithium battery of positive pole with the compound containing lithium, in charge and discharge process, exist without lithium metal, only lithium ion.In 20 generation
Record the beginning of the nineties, Japanese Sony Energy Development Corporations and Canadian Moli energy companies have succeeded in developing new lithium ion respectively
Battery, it is not only functional and environmentally safe.Because it has self discharge more high and low than energy, good cycle, nothing
Memory effect and it is green the advantages that, be current high efficient secondary battery most with prospects and chemical energy storage with fastest developing speed
Power supply.
Lithium ion battery is made up of positive pole, negative pole, barrier film and electrolyte, lithium ion battery success application, and key exists
In the preparation for the negative material for being reversibly embedded in deintercalate lithium ions, preferable lithium ion battery negative material should be able to accommodate
Substantial amounts of Li+, there is higher ionic conductivity and electronic conductivity, and good stability etc., therefore, the research and development property learned
The more preferable novel anode material of energy, and the research in always lithium ion battery negative material field is modified to existing material
Focus.
The lithium ion battery negative material studied at present can be divided mainly into embedded type negative material, alloying type negative material
With three kinds of transformant negative material.Wherein most typically embedded type negative material is carbon material, yet with cycle efficieny it is relatively low,
Voltage with capacity change it is big, lack stable discharge platform；Alloying type negative material theoretical specific capacity and charge density are high,
Intercalation potential is higher, also is difficult to occur the deposition of lithium in the case of high current charge-discharge, will not produce Li dendrite causes battery
Short circuit, have very important significance to high-power component, but cost is higher, and application is narrow；Transformant negative material refers mainly to
Oxide, sulfide, nitride, phosphide and the fluoride of transition metal, wherein g-C3N4Material can because of its layer structure
Graphene-structured is similar to be stripped into, plus carbonitride due to itself having the modulus of elasticity of superelevation and Mohs' hardness,
And have porosity high, the characteristics such as thermal conductivity is good, furtherd investigate in cathode of lithium battery using beginning.Ground in above-mentioned negative material
In terms of studying carefully achievement, Zeng et al. has invented a kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof and has used the material
The lithium ion battery negative material and lithium ion battery of preparation, the Si-C composite material include the porous carbon matrix with hole
Material and it is compounded in these interpore nano-silicon particles of porous carbon matrix material, and silicon nanoparticle in Si-C composite material
Particle diameter be 5-100nm, wherein nanometer silicone content is 10-90wt%.In addition, Li et al., which has invented one kind, is used for cathode of lithium battery
Composite, using by diaminomaleonitrile (DAMN) as dressing agent to graphite oxide carry out N doping method prepare and
Into adding SnCl during N doping4·5H2O, the composite construction of carbonitride and tin oxide is formed by high temperature cabonization, this
Invention uses the SnO of one step hydro thermal method controllable preparation high nitrogen content2/CxNy/ GN composites, by the composite be used for lithium from
Good chemical property, SnO are shown during sub- GND2The nanoscale of particle disperses and its surface and nitrogen-doped graphene
Cross-linked polymeric.But above-mentioned negative material remains the shortcomings of first charge-discharge efficiency is low, high rate during charging-discharging is poor,
And conventional nitridation carbon negative pole material due to its electric conductivity it is poor, the factors such as electron mobility is low are, it is necessary to further be goed deep into
Study to extend its application in lithium ion battery.
The content of the invention
For the shortcomings of existing carbonitride first charge-discharge efficiency is low, high rate during charging-discharging is poor, the present invention proposes one
The negative material and preparation method of kind lithium battery carbonitride carried titanium dioxide.It is characterized in that the conductive nitride carbon materials prepared
Expect that for the carbon material of rich non-graphitized nitrogen, its structure be the class graphene-structured of two dimensional surface, nanometer is improved by high nitrogen-containing
The electrical conductivity and electron mobility of carbonitride, material energy densities are improved using titanium dichloride load.Layer can be given full play to simultaneously
The advantages of shape graphite phase carbon nitride material porosity is high, and thermal conductivity is good, and avoid its electric conductivity poor, electron mobility is low etc. asks
Topic.
Concrete technical scheme of the present invention is as follows：
A kind of preparation method of lithium battery negative material of carbonitride carried titanium dioxide, it is characterized in using melamine and urine
Element, under the conditions of catalyst and methanol, by controlling the reaction condition in addition and each stage stage by stage of urea, two dimension is made
The carbon nitride precursor slurry of class graphene-structured；Then high temperature sintering after slurry is mixed with titanium dioxide, obtains carbonitride
The negative material of carried titanium dioxide；Specific preparation process is as follows：
（1）Melamine and urea are weighed by certain mass ratio, and urea is divided into four parts of quality not etc.：U1、U2、U3
And U4；Butanol, catalyst and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer, and is with mass concentration
30% sodium hydroxide solution adjusts pH value to alkalescence, raises temperature；Then U2 is added, temperature is further raised and is incubated certain
Time；Then using first acid for adjusting pH value to acidity, U3 is added, heat up simultaneously held for some time；Then melamine is added, is dropped
Low temperature reacts certain time, uses sodium hydroxide solution to keep reaction solution as alkalescence in course of reaction；Continue to cool, add U4
Certain time is reacted, and keeps alkalescence；Finally by solution cooling discharging, precursor pulp is obtained；
（2）By step（1）Heated under the precursor pulp decompression state of gained, it is evaporated partial moisture, then with titanium dioxide
Titanium is mixed by certain mass ratio, and is stirred, and adds in Muffle furnace, high temperature sintering is carried out under the protection of nitrogen, is made
Its volume contraction, density increase, finally obtain the negative material of carbonitride carried titanium dioxide.
Preferably, step（1）The mass ratio of the melamine and urea is 1:4~1:3；
Preferably, step（1）The mass fraction of four parts of urea is：U1 is 15 ~ 25 parts, U2 is 25 ~ 35 parts, U3 is 25 ~ 35
Part, U4 are 15 ~ 25 parts；
Preferably, step（1）The addition of the butanol is the 50 ~ 80% of butanol, catalyst and U1 reactant gross mass；
Preferably, step（1）The catalyst is nickel or copper, and its addition is the 2 of butanol, catalyst and U1 reactant gross mass
~4%；
Preferably, step（1）PH value after the addition U1 is adjusted to 8.2 ~ 8.4, and temperature is 68 ~ 72 DEG C；After the addition U2
Holding temperature is 92 ~ 95 DEG C, and soaking time is 28 ~ 35min；PH value during the addition U3 is 4.8 ~ 5.2, holding temperature 95
~ 100 DEG C, soaking time is 30 ~ 40min；After the addition melamine, temperature is reduced to 88 ~ 93 DEG C, and the reaction time is 55 ~
65min, pH value are 8 ~ 8.5；Reaction temperature after the addition U4 is 70 ~ 80 DEG C, and the reaction time is 12 ~ 18min；
Preferably, step（1）The drop temperature is 35 ~ 45 DEG C；
Preferably, step（2）The moisture content of the slurry should be reduced to less than 10%；The mass ratio of the slurry and titanium dioxide
Example is 3:1~4:1；
Preferably, step（2）The sintering temperature is 300 ~ 350 DEG C.
The negative material of a kind of lithium battery carbonitride carried titanium dioxide, it is characterized in that being prepared by the above method.
By controlling the reaction condition in addition and each stage stage by stage of urea, before the carbonitride of two-dimentional class graphene-structured has been made
Drive somaplasm material；Then high temperature sintering after slurry is mixed with titanium dioxide, the negative material of carbonitride carried titanium dioxide is obtained；
The class graphene-structured of two dimensional surface, its higher nitrogen content ensure that the electrical conductivity and electron mobility of material so that material
With preferable charge-discharge performance and cycle performance.By the addition of titanium dioxide, the energy density of material is improved, battery
Specific capacity increase.
In the preparation process of presoma, the dosage control of melamine is particularly important.When its dosage increase, material
Shear strength, modulus of elasticity and Mohs' hardness increase therewith, and when its content is higher, increase becomes unobvious, therefore, melamine
The dosage of amine is preferably in appropriate scope.Furthermore with the increase of melamine dosage, the adhesive property of gained slurry strengthens,
With titanium dioxide it is compound after, the enhancing of bonding force between two-phase, be advantageous to the raising of composite properties.In addition, three
Poly cyanamid has certain cushioning effect to the pH value of solution, can reduce the acid-base property fluctuation in course of reaction, and increase forerunner
The storage stability of somaplasm material.Urea is added stage by stage, there is the control using reaction condition such as temperature, pH value, and it is controllable
Reaction speed processed and reaction process.The reaction temperature in each stage and time, the pH value of system all should strictly be controlled, must could expired
The class graphene-structured of the two dimensional surface of prestige.Before sintering, answer heating under reduced pressure to evaporate the partial moisture in slurry, burnt with shortening
The time is tied, and reduces surface blisters phenomenon caused by removal of bubbles in sintering process.For anti-oxidation, whole sintering process should be
Carried out under the protection of nitrogen.
It is and existing the invention provides the negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide
The characteristics of technology is compared, and it is protruded and excellent effect are：
1. the reaction condition in addition and each stage of the invention stage by stage by controlling urea, the class graphene knot of two dimension is made
The carbon nitride precursor slurry of structure, obtained nano silicon nitride carbon have the class graphene-structured of two dimensional surface, and its higher nitrogen contains
Amount ensure that the electrical conductivity and electron mobility of material so that material has preferable charge-discharge performance and cycle performance.
2. negative material prepared by the present invention, by the addition of titanium dioxide, the energy density of material is improved, battery
Specific capacity increase.
3. negative material prepared by the present invention, there is good modulus of elasticity and Mohs' hardness, good mechanical performance.
4. the preparation method of the present invention, reaction condition is gentle, easy to control, and cost is appropriate, can reach preferable cost performance.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide, the detailed process that it is prepared are as follows：
10kg melamines and 30kg urea are weighed, and urea is pressed 2:3:3:2 mass ratio be divided into quality not wait four parts of U1,
U2, U3 and U4.24kg butanol, 1.2kg nickel powders and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer, and
PH value is adjusted to 8.4 with the sodium hydroxide solution that mass concentration is 30%, and raises temperature to 68 DEG C.Then U2 is added, further
Rise temperature to 95 DEG C and is incubated 35min.Then pH value is adjusted to 4.8 using formic acid, adds U3, be warming up to 100 DEG C and be incubated
40min.Then add melamine, reduce temperature to 88 DEG C of reaction 65min, kept in course of reaction using sodium hydroxide solution
Reaction solution pH value is 8.Continue to be cooled to 70 DEG C, add U4 reaction 18min, and keep alkalescence.Solution is finally cooled to 45 DEG C
After discharge, obtain precursor pulp；It will be heated under the precursor pulp decompression state of gained, it is evaporated partial moisture, contain
Water rate is down to less than 10%, then takes 30kg slurries to be mixed with 10kg titanium dioxide, and stirs, and adds in Muffle furnace, in nitrogen
Protection under in 350 DEG C carry out high temperature sinterings, make its volume contraction, density increase, finally obtain carbonitride carried titanium dioxide
Negative material.
The negative material of the carbonitride carried titanium dioxide obtained to embodiment 1, lithium manganate battery assembling is used it for,
Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks are protected
The data in holdup and charging interval are as shown in table 1.It can be seen that the negative material of carbonitride carried titanium dioxide produced by the present invention is used
When lithium battery, compared with common lithium battery, have in the performances such as internal resistance, monomer capacity, cycle-index and quick charge bright
Aobvious lifting.
Embodiment 2
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide, the detailed process that it is prepared are as follows：
10kg melamines and 40kg urea are weighed, and urea is pressed 2:3:3:2 mass ratio be divided into quality not wait four parts of U1,
U2, U3 and U4.30kg butanol, 1.5kg copper powders and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer, and
PH value is adjusted to 8.4 with the sodium hydroxide solution that mass concentration is 30%, and raises temperature to 70 DEG C.Then U2 is added, further
Rise temperature to 94 DEG C and is incubated 32min.Then pH value is adjusted to 5.2 using formic acid, adds U3, be warming up to 95 DEG C and be incubated
40min.Then add melamine, reduce temperature to 90 DEG C of reaction 65min, kept in course of reaction using sodium hydroxide solution
Reaction solution pH value is 8.5.Continue to be cooled to 70 DEG C, add U4 reaction 15min, and keep alkalescence.Solution is finally cooled to 35
Discharged after DEG C, obtain precursor pulp；It will be heated under the precursor pulp decompression state of gained, it is evaporated partial moisture,
Moisture content is down to less than 10%, then takes 32kg slurries to be mixed with 10kg titanium dioxide, and stirs, and adds in Muffle furnace, in nitrogen
High temperature sintering is carried out in 350 DEG C under the protection of gas, makes its volume contraction, density increase, finally obtains carbonitride load titanium dioxide
The negative material of titanium.
The negative material of the carbonitride carried titanium dioxide obtained to embodiment 2, lithium manganate battery assembling is used it for,
Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks are protected
The data in holdup and charging interval are as shown in table 1.It can be seen that the negative material of carbonitride carried titanium dioxide produced by the present invention is used
When lithium battery, compared with common lithium battery, have in the performances such as internal resistance, monomer capacity, cycle-index and quick charge bright
Aobvious lifting.
Embodiment 3
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide, the detailed process that it is prepared are as follows：
10kg melamines and 32kg urea are weighed, and urea is pressed 2:3:3:2 mass ratio be divided into quality not wait four parts of U1,
U2, U3 and U4.25kg butanol, 1.25kg nickel powders and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer, and
PH value is adjusted to 8.2 with the sodium hydroxide solution that mass concentration is 30%, and raises temperature to 68 DEG C.Then U2 is added, further
Rise temperature to 95 DEG C and is incubated 28min.Then pH value is adjusted to 5 using formic acid, adds U3, be warming up to 98 DEG C and be incubated
35min.Then add melamine, reduce temperature to 93 DEG C of reaction 60min, kept in course of reaction using sodium hydroxide solution
Reaction solution pH value is 8.5.Continue to be cooled to 75 DEG C, add U4 reaction 12min, and keep alkalescence.Solution is finally cooled to 35
Discharged after DEG C, obtain precursor pulp；It will be heated under the precursor pulp decompression state of gained, it is evaporated partial moisture,
Moisture content is down to less than 10%, then takes 35kg slurries to be mixed with 10kg titanium dioxide, and stirs, and adds in Muffle furnace, in nitrogen
High temperature sintering is carried out in 320 DEG C under the protection of gas, makes its volume contraction, density increase, finally obtains carbonitride load titanium dioxide
The negative material of titanium.
The negative material of the carbonitride carried titanium dioxide obtained to embodiment 3, lithium manganate battery assembling is used it for,
Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks are protected
The data in holdup and charging interval are as shown in table 1.It can be seen that the negative material of carbonitride carried titanium dioxide produced by the present invention is used
When lithium battery, compared with common lithium battery, have in the performances such as internal resistance, monomer capacity, cycle-index and quick charge bright
Aobvious lifting.
Embodiment 4
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide, the detailed process that it is prepared are as follows：
10kg melamines and 34kg urea are weighed, and urea is pressed 2:3:3:2 mass ratio be divided into quality not wait four parts of U1,
U2, U3 and U4.26kg butanol, 1.3kg copper powders and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer, and
PH value is adjusted to 8.2 with the sodium hydroxide solution that mass concentration is 30%, and raises temperature to 72 DEG C.Then U2 is added, further
Rise temperature to 95 DEG C and is incubated 35min.Then pH value is adjusted to 4.8 using formic acid, adds U3, be warming up to 98 DEG C and be incubated
32min.Then add melamine, reduce temperature to 88 DEG C of reaction 58min, kept in course of reaction using sodium hydroxide solution
Reaction solution pH value is 8.Continue to be cooled to 78 DEG C, add U4 reaction 14min, and keep alkalescence.Solution is finally cooled to 38 DEG C
After discharge, obtain precursor pulp；It will be heated under the precursor pulp decompression state of gained, it is evaporated partial moisture, contain
Water rate is down to less than 10%, then takes 38kg slurries to be mixed with 10kg titanium dioxide, and stirs, and adds in Muffle furnace, in nitrogen
Protection under in 340 DEG C carry out high temperature sinterings, make its volume contraction, density increase, finally obtain carbonitride carried titanium dioxide
Negative material.
The negative material of the carbonitride carried titanium dioxide obtained to embodiment 4, lithium manganate battery assembling is used it for,
Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks are protected
The data in holdup and charging interval are as shown in table 1.It can be seen that the negative material of carbonitride carried titanium dioxide produced by the present invention is used
When lithium battery, compared with common lithium battery, have in the performances such as internal resistance, monomer capacity, cycle-index and quick charge bright
Aobvious lifting.
Embodiment 5
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide, the detailed process that it is prepared are as follows：
10kg melamines and 36kg urea are weighed, and urea is pressed 2:3:3:2 mass ratio be divided into quality not wait four parts of U1,
U2, U3 and U4.27.5kg butanol, 1.4kg nickel powders and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer,
And pH value is adjusted to 8.3 with the sodium hydroxide solution that mass concentration is 30%, and temperature is raised to 69 DEG C.Then U2 is added, enters one
Step rise temperature to 94 DEG C and is incubated 33min.Then pH value is adjusted to 5 using formic acid, adds U3, be warming up to 98 DEG C and be incubated
38min.Then add melamine, reduce temperature to 90 DEG C of reaction 60min, kept in course of reaction using sodium hydroxide solution
Reaction solution pH value is 8.2.Continue to be cooled to 72 DEG C, add U4 reaction 16min, and keep alkalescence.Solution is finally cooled to 42
Discharged after DEG C, obtain precursor pulp；It will be heated under the precursor pulp decompression state of gained, it is evaporated partial moisture,
Moisture content is down to less than 10%, then takes 40kg slurries to be mixed with 10kg titanium dioxide, and stirs, and adds in Muffle furnace, in nitrogen
High temperature sintering is carried out in 360 DEG C under the protection of gas, makes its volume contraction, density increase, finally obtains carbonitride load titanium dioxide
The negative material of titanium.
The negative material of the carbonitride carried titanium dioxide obtained to embodiment 5, lithium manganate battery assembling is used it for,
Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks are protected
The data in holdup and charging interval are as shown in table 1.It can be seen that the negative material of carbonitride carried titanium dioxide produced by the present invention is used
When lithium battery, compared with common lithium battery, have in the performances such as internal resistance, monomer capacity, cycle-index and quick charge bright
Aobvious lifting.
Embodiment 6
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide, the detailed process that it is prepared are as follows：
10kg melamines and 38kg urea are weighed, and urea is pressed 2:3:3:2 mass ratio be divided into quality not wait four parts of U1,
U2, U3 and U4.28kg butanol, 1.5kg copper powders and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer, and
PH value is adjusted to 8.2 with the sodium hydroxide solution that mass concentration is 30%, and raises temperature to 72 DEG C.Then U2 is added, further
Rise temperature to 92 DEG C and is incubated 35min.Then pH value is adjusted to 4.8 using formic acid, adds U3, be warming up to 100 DEG C and be incubated
35min.Then add melamine, reduce temperature to 90 DEG C of reaction 55min, kept in course of reaction using sodium hydroxide solution
Reaction solution pH value is 8.2.Continue to be cooled to 72 DEG C, add U4 reaction 15min, and keep alkalescence.Solution is finally cooled to 40
Discharged after DEG C, obtain precursor pulp；It will be heated under the precursor pulp decompression state of gained, it is evaporated partial moisture,
Moisture content is down to less than 10%, then takes 36kg slurries to be mixed with 10kg titanium dioxide, and stirs, and adds in Muffle furnace, in nitrogen
High temperature sintering is carried out in 330 DEG C under the protection of gas, makes its volume contraction, density increase, finally obtains carbonitride load titanium dioxide
The negative material of titanium.
The negative material of the carbonitride carried titanium dioxide obtained to embodiment 6, lithium manganate battery assembling is used it for,
Under the test condition that 1C chargings, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks are protected
The data in holdup and charging interval are as shown in table 1.It can be seen that the negative material of carbonitride carried titanium dioxide produced by the present invention is used
When lithium battery, compared with common lithium battery, have in the performances such as internal resistance, monomer capacity, cycle-index and quick charge bright
Aobvious lifting.
Comparative example 1
The negative material and preparation method of a kind of lithium battery carbonitride carried titanium dioxide, the detailed process that it is prepared are as follows：
10kg melamines and 38kg urea are weighed, 28kg is added in the reactor equipped with agitator, condenser pipe and thermometer
Butanol, 1.5kg copper powders and urea, and pH value is adjusted to 8.2 with the sodium hydroxide solution that mass concentration is 30%, and raise temperature
To 72 DEG C.Further rise temperature to 92 DEG C and is incubated 35min.Then pH value is adjusted to 4.8 using formic acid, is warming up to 100 DEG C
And it is incubated 35min.Then add melamine, reduce temperature to 90 DEG C of reaction 55min, it is molten using sodium hydroxide in course of reaction
It is 8.2 that liquid, which keeps reaction solution pH value,.Continue to be cooled to 72 DEG C, react 15min, and keep alkalescence.Solution is finally cooled to 40
Discharged after DEG C, obtain precursor pulp；It will be heated under the precursor pulp decompression state of gained, it is evaporated partial moisture,
Moisture content is down to less than 10%, then takes 36kg slurries to be mixed with 10kg titanium dioxide, and stirs, and adds in Muffle furnace, in nitrogen
High temperature sintering is carried out in 330 DEG C under the protection of gas, makes its volume contraction, density increase, finally obtains carbonitride load titanium dioxide
The negative material of titanium.
The negative material for the carbonitride carried titanium dioxide that comparative example 1 obtains, lithium manganate battery assembling is used it for, in 1C
Under the test condition that charging, 10C discharge, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capacity after 500 weeks are kept
Rate and the data in charging interval are as shown in table 1.
Comparative example 2
From the commercially available graphite cathode material of state's pavilion high-tech, lithium manganate battery assembling is used it for, in 1C chargings, the survey of 10C electric discharges
Under the conditions of examination, circulate 500 weeks, the obtained internal resistance of cell, monomer capacity, the capability retention after 500 weeks and the number in charging interval
According to as shown in table 1.
By embodiment 1-6, comparative example 1-2 negative material and lithium manganate cathode, lithium battery is assembled under the conditions of of the same race, is entered
Row performance comparison is analyzed, such as table 1.
Table 1：
Claims (10)
1. a kind of lithium battery preparation method of the negative material of carbonitride carried titanium dioxide, be characterized in using melamine with
Urea, under the conditions of catalyst and methanol, by controlling the reaction condition in addition and each stage stage by stage of urea, two dimension is made
Class graphene-structured carbon nitride precursor slurry；Then high temperature sintering after slurry is mixed with titanium dioxide, is nitrogenized
The negative material of carbon carried titanium dioxide；Specific preparation process is as follows：
（1）Melamine and urea are weighed by certain mass ratio, and urea is divided into four parts of quality not etc.：U1、U2、U3
And U4；Butanol, catalyst and U1 are added in the reactor equipped with agitator, condenser pipe and thermometer, and is with mass concentration
30% sodium hydroxide solution adjusts pH value to alkalescence, raises temperature；Then U2 is added, temperature is further raised and is incubated certain
Time；Then using first acid for adjusting pH value to acidity, U3 is added, heat up simultaneously held for some time；Then melamine is added, is dropped
Low temperature reacts certain time, uses sodium hydroxide solution to keep reaction solution as alkalescence in course of reaction；Continue to cool, add U4
Certain time is reacted, and keeps alkalescence；Finally by solution cooling discharging, precursor pulp is obtained；
（2）By step（1）Heated under the precursor pulp decompression state of gained, it is evaporated partial moisture, then with titanium dioxide
Titanium is mixed by certain mass ratio, and is stirred, and adds in Muffle furnace, high temperature sintering is carried out under the protection of nitrogen, is made
Its volume contraction, density increase, finally obtain the negative material of carbonitride carried titanium dioxide.
2. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（1）The mass ratio of the melamine and urea is 1:4~1:3.
3. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（1）The mass fraction of four parts of urea is：U1 is 15 ~ 25 parts, U2 is 25 ~ 35 parts, U3 is 25 ~ 35 parts,
U4 is 15 ~ 25 parts.
4. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（1）The addition of the butanol is the 50 ~ 80% of butanol, catalyst and U1 reactant gross mass.
5. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（1）The catalyst is nickel or copper, its addition be butanol, catalyst and U1 reactant gross mass 2 ~
4%。
6. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（1）PH value after the addition U1 is adjusted to 8.2 ~ 8.4, and temperature is 68 ~ 72 DEG C；Protected after the addition U2
Temperature is 92 ~ 95 DEG C, and soaking time is 28 ~ 35min；PH value during the addition U3 is 4.8 ~ 5.2, holding temperature is 95 ~
100 DEG C, soaking time is 30 ~ 40min；After the addition melamine, temperature is reduced to 88 ~ 93 DEG C, and the reaction time is 55 ~
65min, pH value are 8 ~ 8.5；Reaction temperature after the addition U4 is 70 ~ 80 DEG C, and the reaction time is 12 ~ 18min.
7. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（1）The drop temperature is 35 ~ 45 DEG C.
8. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（2）The moisture content of the slurry should be reduced to less than 10%；The mass ratio of the slurry and titanium dioxide
For 3:1~4:1.
9. the preparation method of a kind of lithium battery negative material of carbonitride carried titanium dioxide according to claim 1, its
It is characterised by：Step（2）The sintering temperature is 300 ~ 350 DEG C.
A kind of 10. lithium battery negative material of carbonitride carried titanium dioxide, it is characterized in that by any one of claim 1-9 institutes
The method stated is prepared.
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