CN109449389A - The preparation method of the compound cathode material of lithium ion battery of silicon-carbon - Google Patents
The preparation method of the compound cathode material of lithium ion battery of silicon-carbon Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the compound cathode material of lithium ion battery of silicon-carbon, the following steps are included: (1) takes 65-75 parts of expanded graphites, 25-35 parts of nano silicon particles, 20-30 parts of carbon sources and 750-800 parts of mill balls, then it is sequentially placed into ball mill, agitation grinding 8-10 hours；(2) 750-850 parts of deionized waters and 85-125 parts of dispersing agents are added in the expanded graphite and nano silicon particles that grinding is completed into step (1), are mixed, ball milling 4-6 hours；(3) slurry obtained by step (2) is spray-dried, continuous 5-10 seconds by spraying, the moisture content for reaching mixture is 3-5%；(4) it is spray-dried again, makes water less than 0.1%；(5) material after drying is subjected to selection by winnowing removal of impurities.Preparation method of the invention has that nano silicon particles are uniform stable is coated between expanded graphite lamella, good cycle, again forthright high advantage.
Description
Technical field
The present invention relates to lithium ion battery negative material preparation technical fields, more specifically, it relates to which a kind of silicon-carbon is multiple
The preparation method of mould assembly cathode material of lithium ion battery.
Background technique
Lithium ion battery theoretical specific capacity with higher, longer cycle life and it is highly-safe the advantages that, answer extensively
For in portable electronic device, such as mobile phone, computer, digital camera.Commercialized graphite as anode material for lithium-ion battery tool
There are lower lithium storage content (theoretical specific capacity 372mAh/g) and poor high rate performance, is unable to satisfy large-scale energy storage device
Energy requirement.Therefore, research and development have high capacity, the lithium ion battery negative material of long circulation life particularly important.Silicon because its compared with
The advantages that high theoretical specific capacity (4200mAh/g), lower charging/discharging voltage and rich reserves, cause numerous researchers'
Pay attention to.But silicon materials lithium ion be embedded in and deviate from when there are serious volume change (big 300%) and silicon materials itself
The problems such as poor electric conductivity, leads to its poor cyclical stability and high rate performance, limit its commercialized application.
According to silicon-based anode there are the problem of, design new structural silicon based composite material to buffer the body of nano silicon particles
Product variation keeps the dusting of the integrality and reduction electrode material of electrode structure during charge/discharge to become particularly important.
Currently, there are many silicon substrate lithium ion battery of structure, such as fibre structure, nucleocapsid structure, silicon/carbon, metal composite structure for report
Deng.Recently, expanded graphite is due to its two-dimensional structure with relatively thin Nano graphite lamella, higher electric conductivity, porosity and compared with
Low cost is gradually considered as the building ideal carbon material of silicon/carbon nanometer combined electrode.Expanded graphite and silicon materials compound one
Aspect can buffer the volume change of silicon, improve the stability of silicon electrode material, and another aspect expanded graphite can significantly improve
The conductivity of electrode material improves the charge-discharge performance of electrode material.
Currently, the preparation method of expanded graphite modified silicon based anode material is usually to be received using simple expanded graphite with silicon
Rice grain mixing, while carbon source is introduced, or the dispersion of expanded graphite lamella is improved using the method for ball milling and then improves expansion
The mixing of graphite and nano silicon particles.But these preparation methods have the disadvantage in that
1, there are the reunions of silicon nanometer and expanded graphite and nano silicon particles to mix uneven etc. ask for simple physical mixed
Topic.
Although 2, improving the degree of mixing of expanded graphite and nano silicon particles to a certain extent by the method for ball milling,
Due to the binding force of nano silicon particles and expanded graphite deficiency, cause in charge and discharge process nano silicon particles from expanded graphite lamella
In fall off.
Summary of the invention
In view of the deficienciess of the prior art, the first purpose of this invention is to provide a kind of compound lithium ion of silicon-carbon
The preparation method of negative electrode battery material, having can make nano silicon particles are uniform stable to be coated on expanded graphite lamella
Between, good cycle, again forthright high advantage.
To realize above-mentioned first purpose, the present invention provides the following technical scheme that a kind of compound lithium-ion electric of silicon-carbon
The preparation method of pond negative electrode material, which comprises the following steps: (1) take 65-75 parts of expanded graphites, 25-35 parts of silicon
Nano particle, 20-30 part carbon source and 750-800 parts of mill balls, are then sequentially placed into ball mill, and agitation grinding 8-10 hours；
(2) 750-850 parts of deionized waters and 85- is added in the expanded graphite and nano silicon particles that grinding is completed into step (1)
125 parts of dispersing agents are mixed, ball milling 4-6 hours；
(3) slurry obtained by step (2) is spray-dried, continuous 5-10 seconds by spraying, the moisture content for reaching mixture is 3-
5%；(4) it is spray-dried again, makes water less than 0.1%；
(5) material after drying is subjected to selection by winnowing removal of impurities.
By using above-mentioned technical proposal, since expanded graphite and nano silicon particles are ground and being divided using ball-milling method
It dissipates, using strong shock, grinding and stirring, the partial size that expanded graphite and nano silicon particles are ground is smaller, obtains higher
Specific surface area is added dispersing agent and deionized water, so that expanded graphite and nano silicon particles is uniformly dispersed, nano silicon particles after grinding
The surface of expanded graphite is not adhered to only, after in the hole inside expanded graphite, reusing spray drying to mixing
Expanded graphite and nano silicon particles be dried, the hot gas for being spray-dried ejection can remove moisture, shrink expanded graphite,
The intrapore nano silicon particles cladding of expanded graphite will be located at wherein, increase the binding force of nano silicon particles and expanded graphite,
Prevent the nano silicon particles in charge and discharge process from falling off from expanded graphite lamella, the compound lithium ion battery of raising silicon-carbon is used negative
The cycle performance of pole material and forthright again.
Further, the dispersing agent by following parts by weight material composition: 15-20 parts of N-Methyl pyrrolidones, 6-10
Part polyvinyl alcohol, 3-8 parts of neopelexes, 2-5 parts of n,N-Dimethylformamide, 3-7 parts of alcohol and 4-9 parts of chlorinations
Iron.
Expanded graphite, quick insertion can be removed due to using N-Methyl pyrrolidone by using above-mentioned technical proposal
Expansible graphite interlayer, and expand, increase expanded graphite interlamellar spacing, weaken interlayer Van der Waals force, increases expanded graphite interlamellar spacing
From the embedding lithium capacity of promotion electrode material, while the buffering matrix as silicon electrode to a certain extent accommodates nano silicon particles
Spray and contraction in charge and discharge process, improve the annular stability and high rate performance of electrode material；Alcohol can promote
Into the dispersion of expanded graphite, expanded graphite can be made to be uniformly dispersed, at this time neopelex and N, N- dimethyl formyl
Amine cooperates, and expanded graphite and nano silicon particles can be uniformly dispersed.
Further, 20-30 parts of phosphor tins are added in the step (1) before grinding into ball mill.
By using above-mentioned technical proposal, phosphor tin can alleviate expanded graphite volume expansion and electrochemistry is prevented to reunite
Effect, be a kind of ion battery cathode material of function admirable, realize expanded graphite to phosphor tin by the method for ball milling
Cladding, the overall conductivity of electrode material can not only be increased, moreover it is possible to alleviate the volume expansion of expanded graphite.
Further, the phosphor tin is Sn3P、SnP、SnP3And Sn4P3One or more of mixture.
By using above-mentioned technical proposal, tin and phosphorus can generate synergistic effect, and the high conductivity of metallic tin can improve
The electrical insulation property of phosphorus, and P elements can dispersed metal tin particles, alleviate expanded graphite volume expansion, and prevent electrochemistry
Reunion, and due to Sn4P3There is relatively large irreversible specific capacity, lithium during charge and discharge cycles when discharging for the first time
Being embedded in abjection material with sodium is that biggish volume change is effectively buffered.
Further, expanded graphite is ground to partial size in the step (1) is 5-8um.
By using above-mentioned technical proposal, partial size is the expanded graphite of 5-8um when being mutually mixed with dispersing agent, Neng Gouchong
Divide and nano silicon particles are coated in the hole of expanded graphite, and is distributed nano silicon particles in the hole of expanded graphite
It is even.
Further, the inlet temperature of the hot-air of the spray dryer is 300-350 DEG C, outlet temperature 25-45
℃。
By using above-mentioned technical proposal, expanded graphite is dried in the hot-air using temperature at 300-350 DEG C, no
It so that expanded graphite moment is shunk shrivelled, nano silicon particles are coated in expanded graphite gap, prevent expanded graphite from existing
It is detached from when charge and discharge with expanded graphite, and temperature can be prevented too high, the thinner expanded graphite of particle, which is reunited, to agglomerate.
Further, the mill ball is zirconia ball, and sphere diameter specification is one of 3mm-30mm or collocation is concentrated to make
With.
By using above-mentioned technical proposal, use zirconia ball as mill ball, and the use of sphere diameter is in 3mm-30mm
One or more collocation, can make the mill ball of different-grain diameter grind expanded graphite, increase expanded graphite and mill ball
Contact area, make expanded graphite grinding it is thinner.
Further, the revolving speed of the ball mill is 300-400 revs/min.
By using above-mentioned technical proposal, expanded graphite is ground using the ball mill that revolving speed is 300-400 revs/min
Mill can make expanded graphite grinding thinner, and be uniformly mixed expanded graphite and nano silicon particles.
Further, the step (3) is dried in vacuo slurry, drying temperature is before being spray-dried
80-90℃。
By using above-mentioned technical proposal, expanded graphite and nano silicon particles are dried using vacuum drying, and temperature
Degree is at 80-90 DEG C, because expanded graphite particles are thinner, if temperature is higher, is easy reunite agglomeration, if temperature is lower, rate of drying
It is relatively slow, influence drying efficiency.
Further, deionization moisture 4-5 times addition, each additional amount account for ionized water total weight in the step (2)
20-25%.
By using above-mentioned technical proposal, deionized water is added portionwise, can be sufficiently by expanded graphite and nano silicon particles
It is uniformly mixed, is evenly coated at nano silicon particles in the hole of expanded graphite.
In conclusion the invention has the following advantages:
The first, the present invention uses reasonable ball-milling method, and using zirconia ball as mill ball, due to zirconium oxide ball warp not
It together, can obtain smaller than common graphite class conductive agent partial size, the compound lithium ion battery of the higher silicon-carbon of specific surface area is with negative
Pole material, while mixed expanded graphite and nano silicon particles are dried using spray drying process, it being capable of wink-dry
Nano silicon particles are coated in the hole of expanded graphite by moisture, thus increase the binding force of nano silicon particles and expanded graphite,
To improve the cycle performance of electrode material and forthright again.
The second, preferably using N-Methyl pyrrolidone as dispersing agent in the present invention, since N-Methyl pyrrolidone has
Excellent dissolubility can cooperate with alcohol, expanded graphite and nano silicon particles is made to be uniformly dispersed in mixed process, and
N-Methyl pyrrolidone can make nano silicon particles uniform adhesion in the surface of expanded graphite and the hole of expanded graphite, thus
Preferable binding force is obtained, the cycle performance of electrode material and forthright again is increased.
Third, the present invention are by being added phosphor tin in grinding, capable of alleviating expanded graphite volume expansion and preventing electricity
The effect of chemical agglomeration cooperates by way of with ball milling, can be realized expanded graphite to the cladding of phosphor tin, not only
The overall conductivity of electrode material can be increased, moreover it is possible to alleviate the volume expansion of expanded graphite.
Detailed description of the invention
Fig. 1 is the edge thickness of expanded graphite after ball milling in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the expanded graphite and nano silicon particles after dispersing in embodiment 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of expanded graphite and nano silicon particles after being spray-dried in embodiment 1；
Fig. 4 be Application Example 1-4 made from the compound cathode material of lithium ion battery of silicon-carbon as electrode material lithium from
The cycle performance test result curve graph of sub- battery；
Fig. 5 is lithium-ion electric of the compound cathode material of lithium ion battery of silicon-carbon as electrode material made from embodiment 1-4
The high rate performance test result curve graph in pond.
Specific embodiment
Below in conjunction with drawings and examples, invention is further described in detail.
One, the preparation example 1-3 of dispersing agent
Preparation example 1: taking 15kgN- methyl pyrrolidone and 6kg polyvinyl alcohol, be put into reactor and stir evenly, then successively to anti-
It answers and 3kg neopelex and 2kgN, dinethylformamide, 2kg alcohol and 4kg iron chloride is added in device.
Preparation example 2: 17kgN- methyl pyrrolidone and 8kg polyvinyl alcohol are taken, is put into reactor and stirs evenly, then successively
5kg neopelex and 4kgN, dinethylformamide, 5kg alcohol and 6kg iron chloride are added into reactor.
Preparation example 3: taking 20kgN- methyl pyrrolidone and 10kg polyvinyl alcohol, be put into reactor and stir evenly, then according to
It is secondary that 8kg neopelex and 5kgN, dinethylformamide, 7kg alcohol and 9kg iron chloride are added into reactor.
Two, embodiment 1-4:
A kind of embodiment 1: preparation method of the compound cathode material of lithium ion battery of silicon-carbon, comprising the following steps: (1) take
65kg expanded graphite, 35kg nano silicon particles, 30kg carbon source and 750kg mill ball, are then sequentially placed into ball mill, then to ball
20kg phosphor tin is added in grinding machine, agitation grinding 8 hours, the revolving speed of ball mill was 300 revs/min, and expanded graphite is ground
It is 5um to partial size, referring to Fig. 1, the edge thickness of the expanded graphite after grinding is 80-120nm；
Mill ball is zirconia ball, and sphere diameter specification is 3mm；Phosphor tin is Sn3P、SnP、SnP3And Sn4P3Mixture；
(2) 750kg deionized water and 85kg dispersion are added in the expanded graphite and nano silicon particles that grinding is completed into step (1)
Agent is mixed, ball milling 4 hours, and the revolving speed of ball mill is 300 revs/min, expanded graphite and nano silicon particles ginseng after dispersion
See Fig. 2；
Deionization moisture 4 times additions, each additional amount account for the 25% of ionized water total weight；
(3) slurry obtained by step (2) being dried in vacuo, drying temperature is 80 DEG C, then is spray-dried, continuously by spraying 5
Second, the moisture content for reaching mixture is 3%, and the inlet temperature of the hot-air of spray dryer is 300 DEG C, outlet temperature 25
℃；
(4) it being spray-dried again, makes water less than 0.1%, the inlet temperature of the hot-air of spray dryer is 300 DEG C,
Outlet temperature is 25 DEG C, and the cladding degree of expanded graphite and nano silicon particles is referring to Fig. 3 after spray drying；
(5) material after drying is subjected to selection by winnowing removal of impurities.
A kind of embodiment 2: preparation method of the compound cathode material of lithium ion battery of silicon-carbon, comprising the following steps: (1)
70kg expanded graphite, 30kg nano silicon particles, 25kg carbon source and 780kg mill ball are taken, is then sequentially placed into ball mill, then to
25kg phosphor tin is added in ball mill, agitation grinding 9 hours, the revolving speed of ball mill was 350 revs/min, and expanded graphite is ground
Being milled to partial size is 6um；
Mill ball is zirconia ball, and sphere diameter specification is 15mm；Phosphor tin is Sn3P、SnP、SnP3And Sn4P3Mixture；
(2) 800kg deionized water and 105kg points is added in the expanded graphite and nano silicon particles that grinding is completed into step (1)
Powder is mixed, ball milling 5 hours, and the revolving speed of ball mill is 350 revs/min；
Deionization moisture 5 times additions, each additional amount account for the 20% of ionized water total weight；
(3) slurry obtained by step (2) being dried in vacuo, drying temperature is 85 DEG C, then is spray-dried, continuously by spraying 7
Second, the moisture content for reaching mixture is 4%, and the inlet temperature of the hot-air of spray dryer is 330 DEG C, outlet temperature 35
℃；
(4) it being spray-dried again, makes water less than 0.1%, the inlet temperature of the hot-air of spray dryer is 330 DEG C,
Outlet temperature is 35 DEG C；
(5) material after drying is subjected to selection by winnowing removal of impurities.
A kind of embodiment 3: preparation method of the compound cathode material of lithium ion battery of silicon-carbon, comprising the following steps: (1)
75kg expanded graphite, 25kg nano silicon particles, 30kg carbon source and 800kg mill ball are taken, is then sequentially placed into ball mill, then to
30kg phosphor tin is added in ball mill, agitation grinding 10 hours, the revolving speed of ball mill was 400 revs/min, and expanded graphite is ground
Being milled to partial size is 8um；
Mill ball is zirconia ball, and sphere diameter specification is 30mm；Phosphor tin is Sn3P、SnP、SnP3And Sn4P3Mixture；
(2) 800kg deionized water and 125kg points is added in the expanded graphite and nano silicon particles that grinding is completed into step (1)
Powder is mixed, ball milling 6 hours, and the revolving speed of ball mill is 400 revs/min；
Deionization moisture 5 times additions, each additional amount account for the 20% of ionized water total weight；
(3) slurry obtained by step (2) being dried in vacuo, drying temperature is 90 DEG C, then is spray-dried, continuously by spraying 10
Second, the moisture content for reaching mixture is 5%, and the inlet temperature of the hot-air of spray dryer is 350 DEG C, outlet temperature 45
℃；
(4) it being spray-dried again, makes water less than 0.1%, the inlet temperature of the hot-air of spray dryer is 350 DEG C,
Outlet temperature is 45 DEG C；
(5) material after drying is subjected to selection by winnowing removal of impurities.
A kind of embodiment 4: preparation method of the compound cathode material of lithium ion battery of silicon-carbon, comprising the following steps: (1)
65kg expanded graphite, 35kg nano silicon particles, 30kg carbon source and 750kg mill ball are taken, is then sequentially placed into ball mill, then to
20kg phosphor tin is added in ball mill, agitation grinding 8 hours, the revolving speed of ball mill was 300 revs/min, and expanded graphite is ground
Being milled to partial size is 5um；
Mill ball is zirconia ball, and the ball warp of zirconia ball is 3mm and two kinds of 30mm collocation use sphere diameter；Phosphor tin is
Sn3P、SnP、SnP3And Sn4P3Mixture；
(2) 750kg deionized water and 85kg dispersion are added in the expanded graphite and nano silicon particles that grinding is completed into step (1)
Agent is mixed, ball milling 4 hours, and the revolving speed of ball mill is 300 revs/min；
Deionization moisture 4 times additions, each additional amount account for the 25% of ionized water total weight；
(3) slurry obtained by step (2) being dried in vacuo, drying temperature is 80 DEG C, then is spray-dried, continuously by spraying 5
Second, the moisture content for reaching mixture is 3%, and the inlet temperature of the hot-air of spray dryer is 300 DEG C, outlet temperature 25
℃；
(4) it being spray-dried again, makes water less than 0.1%, the inlet temperature of the hot-air of spray dryer is 300 DEG C,
Outlet temperature is 25 DEG C；
(5) material after drying is subjected to selection by winnowing removal of impurities.
Three, comparative example 1-4
Comparative example 1: a kind of preparation method of the compound cathode material of lithium ion battery of silicon-carbon, the difference from embodiment 1 is that,
Dispersing agent is not used in step (2).
Comparative example 2: a kind of preparation method of the compound cathode material of lithium ion battery of silicon-carbon, the difference with embodiment 1
It is, is free of N-Methyl pyrrolidone in step (2) in dispersing agent used.
Comparative example 3: a kind of preparation method of the compound cathode material of lithium ion battery of silicon-carbon, the difference with embodiment 1
It is, deionized water is added at one time in step (2).
Comparative example 4: a kind of preparation method of the compound cathode material of lithium ion battery of silicon-carbon, the difference with embodiment 1
It is, is free of iron chloride in step (2) in contained dispersing agent.
Four, performance detection: cell negative electrode material is prepared according to the method in embodiment 1-4 and comparative example 1-4, according to following
The following performance of standard detection:
1, partial size: Mastersizer2000 detection device is used, according to GB/T19077.1-2003 grain size analysis laser diffractometry
Detection, test result are as shown in table 1；
2, specific surface area: using MonsorbMS-21 detection device, and according to GB/T19587-2004, " gas absorption BET method is measured
Solid matter specific surface area " it measures, test result is as shown in table 1；
3, phosphorus content: using SARTORTUW-BP121S, Muffle Furnace-KSW, according to GB/T3521-2008 " graphitization
Learn analytic approach " it measures, test result is as shown in table 1；
4, it tap density: is detected according to GB/T5162-2006 " measurement of metal powder tap density ", test result such as 1 institute of table
Show；
5, moisture: measuring according to GB/T3521-2008 " graphite chemical analysis ", and test result is as shown in table 1.
The compound cathode material of lithium ion battery the performance test results of silicon-carbon made from each embodiment of table 1 and each comparative example
By data in table 1 it is found that the compound cathode material of lithium ion battery of silicon-carbon prepared using method in embodiment 1-4
D10≤10.343 μm, D50≤16.654 μm, the granularity of D90≤21.764 μm, cathode material of lithium ion battery is thinner,
By the way that compared in the comparative example 1 for not using dispersing agent, D10, D50 and D90 in comparative example 1 are all larger than in an embodiment and survey
Examination value, therefore dispersing agent is used, the partial size of cell negative electrode material becomes smaller；Compared with comparative example 2, because using not in comparative example 2
Dispersing agent containing N-Methyl pyrrolidone, for cell negative electrode material compared with each embodiment, partial size is larger；In same comparative example 3 because
Deionized water is added at one time, and causes the partial size of cell negative electrode material larger；The ratio of cell negative electrode material made from each embodiment
Surface is in 1.47-1.69m2Between/g, tap density is in 0.74-0.78g/cm3Between, phosphorus content 99.97-99.98% it
Between, water content is 0.01%.
Five, application examples 1-2
It is applied to battery cathode and lithium ion by raw material of the compound cathode material of lithium ion battery of silicon-carbon made from embodiment 2
Battery, and lithium ion battery obtained is tested for the property.
Application examples 1: a kind of battery cathode, with the compound cathode material of lithium ion battery of silicon-carbon made from embodiment 2,
The N-Methyl pyrrolidone (PVDF mass percent is 15%) of PVDF is used as bonding agent, and for acetylene black as conductive agent, battery is negative
The ratio of pole material, bonding agent and conductive agent with mass ratio for 96:3:1 is stirred obtained slurry, and the slurry is uniformly applied
It overlays on and battery cathode is made on aluminium foil.
Application examples 2: a kind of lithium ion battery uses in application examples 1 battery cathode obtained as negative electrode material, lithium metal
For piece as anode electrode piece, diaphragm uses polyethylene diagrams, and electrolyte uses LiPF6/ ethylene carbonate+methyl ethyl carbonate+carbon
Dimethyl phthalate (LiPF6/ ethylene carbonate: methyl ethyl carbonate: dimethyl carbonate=1:1:1).Anode electrode piece and negative electrode
Piece is separated using polyethylene diagrams, and injects electrolyte composition button battery, is carried out using button cell of the blue electricity to composition
Performance test, and be compared with the data of comparative example 1-4 test, test result such as table 2.
The performance test results of 2 lithium ion battery of table
Lithium ion battery made from the cell negative electrode material made from Application Example 2 it can be seen from data in table 2 has higher
Discharge capacity for the first time and preferable discharging efficiency, first charge-discharge reversible capacity and cycle performance are preferable for the first time.
Respectively by the compound cathode material of lithium ion battery of silicon-carbon obtained by above-described embodiment 1-4 and conductive black,
Polyacrylic acid is mixed in the ratio of 8:1:1, adds water and stirs and slurry is made, be applied on copper-foil conducting electricity and electrode slice is made, use this
Electrode slice makes lithium ion battery (button cell).Wherein, use lithium piece as to electrode, the lithium ion in the lithium ion battery
The electrolyte of battery is made of dimethyl carbonate, ethylene carbonate and the fluorinated ethylene carbonate that mass ratio is 4.5:4.5:1.It is right
The lithium ion battery of the compound cathode material of lithium ion battery preparation of silicon-carbon made from Application Example 1~3 carries out cyclicity
It can respectively obtain cycle performance test result curve graph (referring to fig. 4) with high rate performance test and high rate performance test result is bent
Line chart (referring to Fig. 5).
As seen from Figure 4, the electrode material of lithium ion battery is under 500mA/g charge and discharge, as made from embodiment 1-4
The average initial mass specific capacity of the compound cathode material of lithium ion battery of silicon-carbon is 2361mAh/g, real after circulation 40 weeks
The average quality specific capacity for applying the compound cathode material of lithium ion battery of silicon-carbon made from a 1-4 is 685mAh/g, mass ratio
Capacity retention ratio is (2361-685)/2361 × 100%=71.0%, shows excellent cyclical stability.
As seen from Figure 5, specific discharge capacity of the lithium ion battery in 100mA/g charge and discharge is 1650mAh/g,
Specific discharge capacity when 200mA/g charge and discharge is 1254mAh/g, and specific discharge capacity when 500mA/g charge and discharge is 1100mAh/
G, the specific discharge capacity in 1A/g charge and discharge is 880mAh/g, shows excellent high rate performance.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (10)
1. a kind of preparation method of the compound cathode material of lithium ion battery of silicon-carbon, which comprises the following steps:
(1) 65-75 parts of expanded graphites, 25-35 parts of nano silicon particles, 20-30 parts of carbon sources and 750-800 parts of mill balls are taken, then successively
It is put into ball mill, agitation grinding 8-10 hours；
(2) 750-850 parts of deionized waters and 85- is added in the expanded graphite and nano silicon particles that grinding is completed into step (1)
125 parts of dispersing agents are mixed, ball milling 4-6 hours；
(3) slurry obtained by step (2) is spray-dried, continuous 5-10 seconds by spraying, the moisture content for reaching mixture is 3-
5%；
(4) it is spray-dried again, makes water less than 0.1%；
(5) material after drying is subjected to selection by winnowing removal of impurities.
2. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon according to claim 1, which is characterized in that
The dispersing agent by following parts by weight material composition: 15-20 parts of N-Methyl pyrrolidones, 6-10 parts of polyvinyl alcohol, 3-8 part ten
Dialkyl benzene sulfonic acids sodium, 2-5 part n,N-Dimethylformamide, 3-7 parts of alcohol and 4-9 parts of iron chloride.
3. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon according to claim 1, which is characterized in that
20-30 parts of phosphor tins are added in the step (1) before grinding into ball mill.
4. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon according to claim 3, which is characterized in that
The phosphor tin is Sn3P、SnP、SnP3And Sn4P3One or more of mixture.
5. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon according to claim 1, which is characterized in that
It is 5-8um that expanded graphite, which is ground to partial size, in the step (1).
6. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon according to claim 1, which is characterized in that
The inlet temperature of the hot-air of the spray dryer is 300-350 DEG C, and outlet temperature is 25-45 DEG C.
7. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon according to claim 1, which is characterized in that
The mill ball is zirconia ball, and sphere diameter specification is one of 3mm-30mm or collocation is concentrated to use.
8. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon described in claim 1, which is characterized in that described
The revolving speed of ball mill is 300-400 revs/min.
9. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon described in claim 1, which is characterized in that described
Step (3) is dried in vacuo slurry before being spray-dried, and drying temperature is 80-90 DEG C.
10. the preparation method of the compound cathode material of lithium ion battery of silicon-carbon described in claim 1, which is characterized in that institute
It states deionization moisture 4-5 times addition, each additional amount in step (2) and accounts for the 20-25% of ionized water total weight.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429265A (en) * | 2019-08-13 | 2019-11-08 | 四川轻化工大学 | A kind of lithium ion battery MEG/Si/C composite negative pole material and preparation method thereof |
| CN110544766A (en) * | 2019-09-23 | 2019-12-06 | 七台河万锂泰电材有限公司 | Expanded graphite nano-silicon composite negative electrode material and preparation method thereof |
| CN111977646A (en) * | 2020-07-20 | 2020-11-24 | 中南大学 | Method for preparing expanded graphite/silicon carbon material from graphite cathode of waste battery |
| CN116759563A (en) * | 2023-08-22 | 2023-09-15 | 浙江煌能新能源科技有限公司 | Porous lithium battery composite anode material, preparation method thereof and lithium battery |
-
2018
- 2018-09-30 CN CN201811158445.7A patent/CN109449389A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429265A (en) * | 2019-08-13 | 2019-11-08 | 四川轻化工大学 | A kind of lithium ion battery MEG/Si/C composite negative pole material and preparation method thereof |
| CN110429265B (en) * | 2019-08-13 | 2021-02-02 | 四川轻化工大学 | MEG/Si/C composite negative electrode material for lithium ion battery and preparation method thereof |
| CN110544766A (en) * | 2019-09-23 | 2019-12-06 | 七台河万锂泰电材有限公司 | Expanded graphite nano-silicon composite negative electrode material and preparation method thereof |
| CN111977646A (en) * | 2020-07-20 | 2020-11-24 | 中南大学 | Method for preparing expanded graphite/silicon carbon material from graphite cathode of waste battery |
| CN116759563A (en) * | 2023-08-22 | 2023-09-15 | 浙江煌能新能源科技有限公司 | Porous lithium battery composite anode material, preparation method thereof and lithium battery |
| CN116759563B (en) * | 2023-08-22 | 2023-12-05 | 浙江煌能新能源科技有限公司 | Porous lithium battery composite anode material, preparation method thereof and lithium battery |
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