A kind of high performance lithium ionic cell cathode material and preparation method thereof
Technical field
The present invention relates to lithium ion battery material preparation technical field, specially a kind of high performance lithium ionic cell cathode material
Material and preparation method thereof.
Background technique
With the rapid development of electric vehicles, it is desirable that lithium ion battery used in electric car have higher energy density and
Higher cycle performance, and negative electrode material is to form the key component of lithium ion battery, the superiority and inferiority of performance is to lithium ion battery
Cycle performance, security performance and its energy density have an important influence on.Negative electrode material used is mainly with graphite currently on the market
Based on class material, but due to its relatively low raising for limiting its energy density of gram volume (372mAh/g).
Currently, the cathode of commercial Li-ion battery mainly uses the carbonaceous materials such as natural graphite, artificial graphite, it is theoretical
Capacity only has 372mAh/g, compares lower, has been unable to meet such as rich lithium material, nickel galaxite high voltage material high-energy
The requirement of positive electrode, also can not meet market to lithium ion cell high-capacity, high circulation performance, high rate capability needs,
Significantly limit the further promotion of battery whole volume.In order to meet the needs of high-capacity lithium ion cell, research and develop
The height ratio capacity negative electrode material of alternative carbon material has become very urgent and necessary.And silicon materials specific volume with higher
Amount, reaches 4200mAh/g, and rich reserves, low in cost, becomes the most promising of substitution natural graphite at present and artificial graphite
Lithium ion battery negative material.However, there are huge volume changes in battery charge and discharge process for pure silicon material, it is this huge
Big volume change will lead to the pole piece dusting of preparation, causes active material to fall off from negative plates, causes electrode activity thing
The separation of matter and collector, to seriously affect the cycle performance of battery;Silicon materials are easily reunited simultaneously, influence the circulation of electrode
Stability limits its extensive use.Although the expansion of material can be reduced by measures such as material nano, material claddings, with
Improve the cycle performance of material.For example patent (CN1036333303A) discloses the lithium ion battery anode material of coating modification,
A kind of lithium ion battery anode material of coating modification, including stratum nucleare and the shell being coated on outside stratum nucleare, stratum nucleare is graphite or silicon
Material, shell are the thermosetting resin that decomposition temperature is greater than 180 DEG C.The surface of core layer material coats thermosetting resin, not only
It can be improved the resistance of anode material, in this way after short circuit occurs between cathode current collector and anode diaphragm, can reduce electric current
Amount reduces heat, improves the security performance of battery.But it be easy to cause analysis to manage, causes it during high rate charge-discharge
Security performance is deteriorated and its high rate performance deviation.Therefore, how on the basis of carbonaceous material and silicon systems material, a kind of gram is developed
Capacity is high, expansion rate is low, good rate capability and its negative electrode material having a safety feature, and is current urgent problem to be solved.
Summary of the invention
Present invention solves the technical problem that being to overcome now, current lithium ion battery negative material gram volume is low, rate energy
And its defect existing for poor safety performance etc., a kind of high performance lithium ionic cell cathode material and preparation method thereof is provided.
Described high performance lithium ionic cell cathode material and preparation method thereof have that gram volume is high, imbibition ability is strong, high rate performance is good and
The features such as its security performance is high.
To achieve the above object, the invention provides the following technical scheme: a kind of high performance lithium ionic cell cathode material and
Core-shell structure is presented in preparation method, lithium ion battery negative material, and kernel is silica, and shell is to contain hexafluoro lithium aluminate
Layer of charcoal;Its outer casing thickness is (50~500) nm;Its preparation process are as follows:
1) configuration of solution A:
It weighs (100~200) g pitch to be dissolved in the organic solvent of 1000g, uniform solution is obtained after being uniformly dissolved, is shifted later
Into glove box, and under an inert gas, then add the hexafluoro of (5~10) g conductive agent, (1~5) g sodium carbonate, (80~90) g
Lithium aluminate, and stir (1~3) h and obtain the hexafluoro lithium aluminate suspension A of stable homogeneous;
2) graphite/hexafluoro lithium aluminate composite material preparation:
After mixing by the hexafluoro lithium aluminate suspension A and (300~500) g silicon materials that prepare in step (1), (50~
DEG C 120) (4~10) h is reacted under conditions of, is obtained silica surface and is coated with hexafluoro lithium aluminate/conductive agent/sodium carbonate stone
Black composite material, is filtered later, and is transferred material into tube furnace, and with the heating of the rate of heating rate (1~10) DEG C min
To (600~800) DEG C, and (1~3) h is kept the temperature, cooled down later, obtaining shell is doped with the more empty hexafluoros of sodium oxide molybdena/conductive agent
Lithium aluminate, kernel are the anode material of graphite.
Preferably, organic solvent in the step (1) are as follows: n-hexane carbon tetrachloride, toluene, dimethylbenzene, in carbon disulfide
One kind.
Preferably, step (1) conductive agent is one of carbon nanotube, gas-phase growth of carbon fibre, mesoporous carbon.
Preferably, step (2) silicon materials are one of silicon monoxide, silica, nano-silicon, the sub- silicon of oxidation.
Compared with prior art, the beneficial effects of the present invention are:
1) hexafluoro lithium aluminate is coated in silica surface, lithium ion battery can be improved in charge and discharge process, lithium ion
Transmission rate, and supplement is provided to form the lithium ion of SEI film consumption in charge and discharge process, improve its circulation, high rate performance.
2) sodium carbonate adulterated in clad decomposes in high-temperature sintering process generates sodium oxide molybdena and carbon dioxide, and leaves
Nano/micron hole can buffer the expansion of silica in charge and discharge process, improve the structural stability of its material, and mention
Its high cycle performance.
3) pitch is dissolved in organic solvent by liquid phase method, and conductive agent, sodium carbonate, hexafluoro lithium aluminate is dissolved in
Wherein it is possible to obtain the mixed liquor of stable homogeneous, and it can be uniformly wrapped on silica surface, improve the consistent of its material
Property.Hexafluoro lithium aluminate is coated on material surface simultaneously, and the high temperature resistance of its material can be improved, improve its security performance.
Detailed description of the invention
Fig. 1 is the SEM figure for the silicon-carbon composite cathode material that the embodiment of the present invention 1 is prepared.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
Referring to Fig. 1, the present invention provides a kind of technical solution: a kind of high performance lithium ionic cell cathode material and its preparation side
Core-shell structure is presented in method, lithium ion battery negative material, and kernel is silica, and shell is the charcoal containing hexafluoro lithium aluminate
Layer;Its outer casing thickness is (50~500) nm;Its preparation process are as follows:
1) configuration of solution A:
It weighs 150g pitch to be dissolved in the n-hexane of 1000g, uniform solution is obtained after being uniformly dissolved, is transferred to glove box later
In, and under an inert gas, then add 8g carbon nanotube, 3g sodium carbonate, 89g hexafluoro lithium aluminate, and stir 2h obtain it is uniform
Stable hexafluoro lithium aluminate suspension A;
2) graphite/hexafluoro lithium aluminate composite material preparation:
After mixing by the hexafluoro lithium aluminate suspension A and 400g silica that are prepared in step (1), under conditions of 80 DEG C
6h is reacted, silica surface is obtained and is coated with hexafluoro lithium aluminate/conductive agent/sodium carbonate graphite composite material, filter later,
And transfer material into tube furnace, and be warming up to 750 DEG C with the rate of 5 DEG C/min of heating rate, and keep the temperature 2h, it drops later
Temperature, obtaining shell is doped with the more empty hexafluoro lithium aluminates of sodium oxide molybdena/conductive agent, and kernel is the cathode composite wood of silica
Material.
Embodiment 2
Core-shell structure is presented in a kind of high performance lithium ionic cell cathode material and preparation method thereof, lithium ion battery negative material,
Kernel is silica, and shell is the layer of charcoal containing hexafluoro lithium aluminate;Its outer casing thickness is (50~500) nm;It was prepared
Journey are as follows:
1) configuration of solution A:
It weighs 100g pitch to be dissolved in the carbon tetrachloride of 1000g, uniform solution is obtained after being uniformly dissolved, is transferred to glove box later
In, and under an inert gas, then the hexafluoro lithium aluminate of 5g gas-phase growth of carbon fibre, 1g sodium carbonate, 90g are added, and stir 1h and obtain
To the hexafluoro lithium aluminate suspension A of stable homogeneous;
2) graphite/hexafluoro lithium aluminate composite material preparation:
After mixing by the hexafluoro lithium aluminate suspension A and 300g silicon monoxide that are prepared in step (1), under conditions of 50 DEG C
10h is reacted, silica surface is obtained and is coated with hexafluoro lithium aluminate/conductive agent/sodium carbonate graphite composite material, later mistake
Filter, and transfer material into tube furnace, and be warming up to 600 DEG C with the rate of 1 DEG C/min of heating rate, and keep the temperature 3h, later
Cooling, obtaining shell is doped with the more empty hexafluoro lithium aluminates of sodium oxide molybdena/conductive agent, and kernel is the cathode composite wood of silicon monoxide
Material.
Embodiment 3
Core-shell structure is presented in a kind of high performance lithium ionic cell cathode material and preparation method thereof, lithium ion battery negative material,
Kernel is silica, and shell is the layer of charcoal containing hexafluoro lithium aluminate;Its outer casing thickness is (50~500) nm;It was prepared
Journey are as follows:
1) configuration of solution A:
It weighs 200g pitch to be dissolved in the organic solvent of 1000g, uniform solution is obtained after being uniformly dissolved, is transferred to glove box later
In, and under an inert gas, then add 10g mesoporous carbon, 5g sodium carbonate, 80g hexafluoro lithium aluminate, and stir 3h obtain it is uniform steady
Fixed hexafluoro lithium aluminate suspension A;
2) graphite/hexafluoro lithium aluminate composite material preparation:
After mixing by the hexafluoro lithium aluminate suspension A and 500g nano-silicon (partial size 50nm) that are prepared in step (1), exist
4h is reacted under conditions of 120 DEG C, obtaining silica surface, to be coated with hexafluoro lithium aluminate/conductive agent/sodium carbonate graphite compound
Material filters later, and transfers material into tube furnace, and is warming up to 800 DEG C with the rate of 10 DEG C of min of heating rate, and
1h is kept the temperature, is cooled down later, obtaining shell is doped with the porous hexafluoro lithium aluminate of sodium oxide molybdena/conductive agent, and kernel is the cathode of silicon
Composite material.
Comparative example
It weighs 100g pitch to be dissolved in the carbon tetrachloride of 1000g, uniform solution is obtained after being uniformly dissolved, add the two of 400g later
Silica after mixing evenly, filters later, and heating removal solvent under conditions of 80 DEG C, later and transfers material into tubular type
In furnace, and 750 DEG C are warming up to the rate of 5 DEG C of min of heating rate, and keep the temperature 2h, cool down later, obtain the silicon of shell carbon coated
Carbon composite.
The following test of design:
SEM test
Fig. 1 is the SEM figure for the silicon-carbon cathode material that embodiment 1 is prepared, and as seen from the figure, chondritic, grain is presented in material
Diameter is 3-6 μm.
Button cell production
Respectively by Examples 1 to 3 and comparative example gained lithium ion battery silicon-carbon cathode material be assembled into button cell A1, A2,
A3 and B1;Preparation method are as follows: add binder, conductive agent and solvent in negative electrode material, be stirred slurrying, be coated in copper
It is obtained by drying, rolling on foil.Binder used is LA132 binder, and conductive agent SP, negative electrode material is Examples 1 to 3
The negative electrode material prepared, solvent are secondary distilled water, its ratio be: negative electrode material: SP:LA132: secondary distilled water=95g:
1g:4g:220ml;Electrolyte is LiPF6/ EC+DEC(1:1), metal lithium sheet is to electrode, and diaphragm uses polyethylene (PE), is gathered
Propylene (PP) or poly- second propylene (PEP) composite membrane, simulated battery are assemblied in the glove box for be flushed with hydrogen gas and carry out, and chemical property exists
It is carried out on the new prestige 5v/10mA type cell tester of the blue electricity in Wuhan, charging/discharging voltage range is 0.005V to 2.0V, charge-discharge velocity
For 0.1C.
It is as shown in table 1 to detain electrical test results.
1 embodiment of table and comparative example buckle electrical test results comparison
Detain electric battery |
A1 |
A2 |
A3 |
B |
Negative electrode material |
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Comparative example |
Discharge capacity (mAh/g) for the first time |
782.4 |
760.1 |
781.7 |
439.5 |
First charge discharge efficiency (%) |
95.1 |
94.8 |
93.3 |
84.4 |
Specific surface area (m2/g) |
6.5 |
6.2 |
6.8 |
3.6 |
As it can be seen from table 1 discharge capacity and efficiency are all using electric battery is detained made from negative electrode material obtained by Examples 1 to 3
It is apparently higher than comparative example.The experimental results showed that negative electrode material of the invention can make battery have good discharge capacity and efficiency;
Reason is: coating one layer of lithium compound on silicon-carbon cathode material surface, the lithium ion for material consumption in charge and discharge process mentions
For lithium ion, to improve its first charge discharge efficiency.
Soft-package battery test
Respectively using embodiment 1, embodiment 2, embodiment 3 and comparative example resulting materials as negative electrode material, it is positive with LiFePO4
Pole material, using LiPF6/ EC+DEC(volume ratio 1:1) it is electrolyte, 2400 film of Celgard is diaphragm, prepares 5AH Soft Roll
Battery C1, C2, C3 and D and its corresponding cathode pole piece, and test the imbibition liquid-keeping property of its cathode pole piece, pole piece rebound
Property, cycle performance and its battery with two side terminals.
The imbibition liquid-keeping property contrast table of 2 different materials of table
Object |
Rate of liquid aspiration (ml/min) |
It protects liquid rate (electrolyte content/0h electrolyte content for 24 hours) |
Embodiment 1 |
5.9 |
91.3% |
Embodiment 2 |
4.8 |
90.2% |
Embodiment 3 |
4.5 |
89.4% |
Comparative example |
2.1 |
83.7% |
From table 2 it can be seen that the imbibition liquid-keeping property of negative electrode material obtained by Examples 1 to 3 is apparently higher than comparative example.Experimental result
Show negative electrode material of the invention imbibition liquid-keeping property with higher, reason is: the sodium carbonate adulterated in clad is in height
It is decomposed in warm sintering process and generates sodium oxide molybdena and carbon dioxide, and leave Nano/micron hole, improve the specific surface of its material
Product, to improve the imbibition liquid-keeping property of its material.
The rebound rate contrast table of 3 pole piece of table
The active material that pole piece uses |
Pole piece rebound rate (%) |
Embodiment 1 |
4.8 |
Embodiment 2 |
5.6 |
Embodiment 3 |
5.1 |
Comparative example |
19.6 |
From table 3 it can be seen that using the cathode pole piece rebound rate of the preparation of negative electrode material obtained by Examples 1 to 3 significantly lower than comparison
Example.The experimental results showed that the negative electrode material gained cathode pole piece using the application has lower rebound rate, reason is: packet
The sodium carbonate adulterated in coating decomposes in high-temperature sintering process generates sodium oxide molybdena and carbon dioxide, and leaves Nano/micron hole
Hole makes its silicon materials provide cushion space in charge and discharge process, reduces its expansion rate.
The circulation of 4 different materials of table compares figure
Battery |
Negative electrode material |
Recycle 500 capacity retention ratios (%) |
C1 |
Embodiment 1 |
92.62 |
C2 |
Embodiment 2 |
91.78 |
C3 |
Embodiment 3 |
90.39 |
D |
Comparative example |
85.55 |
The cycle performance curve graph of the soft-package battery of table 4 gained negative electrode material preparation, in table it can be seen from embodiment battery
Cycle performance is obviously due to comparative example, the reason for this is that being decomposed in high-temperature sintering process using the sodium carbonate adulterated in clad
Sodium oxide molybdena and carbon dioxide are generated, and leaves Nano/micron hole, the expansion of silica in charge and discharge process can be buffered,
The structural stability of its material is improved, and improves its cycle performance
DC internal resistance test and needle pierce short-circuit test
DC internal resistance test: Example 1 ~ 8 and the lithium ion battery of comparative example preparation, test method: referring to " FreedomCAR
Battery testing handbook ".
Needle pierces short-circuit test: Example 1 ~ 8 and the lithium ion battery of comparative example preparation, test method: referring to UL2054
Safety standard testing standard.
The result and performance of DC internal resistance test and needle thorn short-circuit test relatively see the table below 1.
The lithium ion battery direct-current internal resistance test of 5 embodiment of table and comparative example preparation
Compare with the result and performance of needle thorn short-circuit test
As can be seen from Table 5, the security performance of embodiment is substantially better than comparative example, reason are as follows: prepares stabilization by liquid phase method
Hexafluoro lithium aluminate mixed liquor, and silica surface can be uniformly wrapped on, the high temperature resistance of its material can be improved, mention
Its high security performance, while the characteristic that hexafluoro lithium aluminate has lithium ion conducting rate high, reduce the DC internal resistance of its material.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.