CN102891306B - Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof - Google Patents

Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof Download PDF

Info

Publication number
CN102891306B
CN102891306B CN201210407835.XA CN201210407835A CN102891306B CN 102891306 B CN102891306 B CN 102891306B CN 201210407835 A CN201210407835 A CN 201210407835A CN 102891306 B CN102891306 B CN 102891306B
Authority
CN
China
Prior art keywords
methods
lithium ion
nano
cathode material
ion cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210407835.XA
Other languages
Chinese (zh)
Other versions
CN102891306A (en
Inventor
谭强强
段慧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongke (Ma'anshan) New Material Science Park Co., Ltd.
Original Assignee
Institute of Process Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201210407835.XA priority Critical patent/CN102891306B/en
Publication of CN102891306A publication Critical patent/CN102891306A/en
Application granted granted Critical
Publication of CN102891306B publication Critical patent/CN102891306B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method for a lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material. The method comprises the steps that: a lithium titanate material is coated on the surface of a nano-silicon material, so as to form a Si/Li4TiO12 composite; and the Si/Li4TiO12 composite is mixed with carbon nano tubes, so as to obtain a Si/Li4Ti5O12/CNT ternary material by atomizing drying. The negative pole material prepared by using the method disclosed by the invention has high specific capacity and high stability.

Description

A kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material and preparation method thereof
Technical field
The present invention relates to field of electrochemical power source, particularly, the present invention relates to lithium ion battery negative material field.
Background technology
The advantages such as lithium ion battery has compared with traditional secondary cell that open circuit voltage is high, energy density is large, long service life, memory-less effect, pollution-free and self discharge are little, apply more and more extensive.Due to fast development and the extensive use of portable electric appts and electric automobile, the demand for the lithium ion battery of high-energy-density, long circulation life, fast charging and discharging is very urgent.The lithium ion battery negative material of current commercialization is carbon class negative material, but its theoretical capacity is only 372mAh/g, and has developed close to theoretical value.The miniaturization of current various portable electric appts and electric automobile can not be adapted to the widespread demand of large-capacity high-power chemical power source.
Therefore, large quantifier elimination has turned to the Novel anode material system found and can substitute material with carbon element, and wherein silicon is desirable candidate material.Silicon has lot of advantages: rich reserves on the earth, cost are lower, environmental sound; Silicon and lithium can form alloy, have 4 kinds of phase: Li 12si 7, Li 13si 4, Li 7si 3and Li 22si 5; Silicon has higher theoretical specific capacity (Li 22si 5: 4200mAh/g) and lower intercalation potential (vs Li +/ Li), because of but a kind of very rising lithium ion battery negative material.But in charge and discharge process, the removal lithium embedded reaction of silicon, with the change in volume of 310%, easily causes electrode cracking and active material to come off, thus causes electrode cycle penalty.One of thinking addressed this problem is the volumetric expansion of synthesis of silica-base compound, buffer electrode, improves the cyclical stability of electrode.
Li 4ti 5o 12(LTO) there is zero strain characteristic good cycle, intercalation potential is high and not easily cause the advantages such as lithium metal is separated out, security performance is good, anti-over-charging, is one of lithium ion battery negative material of new generation of current most development and application potentiality.But the conductivity of material own is low, have a strong impact on the high power performance of material.
Carbon nano-tube (CNTs) is because having special one-dimentional structure, and the features such as high conductance and good electrochemical stability, be just considered to desirable electrode material, but itself capacity are not high since Iijima finds, limits its application.
CN 101841017A discloses a kind of lithium titanate/carbon/carbon nano-tube combination electrode material and preparation method thereof.Described combination electrode material is made up of lithium titanate, carbon coated and carbon nano-tube, and their mass percent is 90 ~ 97:0 ~ 5:3 ~ 5.Described preparation method with lithium-containing compound, anatase titania and carbon nano-tube for raw material, first lithium titanate/carbon/carbon nano tube compound is prepared by wet chemical method, then adopt organic substance to wrap up obtained lithium titanate/carbon/carbon nano tube compound, under eventually passing inert atmosphere, heat treatment obtains lithium titanate/carbon/carbon nano-tube combination electrode material.But this electrode material can not meet actual needs in high rate performance.
CN 101232094A discloses a kind of lithium ion battery negative pole active materials, and include the first active material A and the second active material B, the first active material A is lithium titanate, has following structural formula: Li 1+xti 2-xo 40≤x≤1/3, the second active material B is that other outside removing lithium titanate can mix/deviate from the active material of lithium, and the second active material B comprises carbon material or alloy material, described carbon material comprises from pyrocarbon, coke, graphite, carbon fiber, carbon nano-tube, carbon gel, activated carbon, carbonaceous mesophase spherules; Described alloy comprises Si base alloy or Sn base alloy.First active material A and the second active material B mass mixing ratio A/ (A+B) are between 0.05-0.5.The anti-over-discharge property of this battery material is excellent, but its high rate performance is undesirable.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of novel composite cathode material for lithium ion cell.Described composite cathode material for lithium ion cell comprises the composite particles be made up of lithium titanate clad nano silicon and the carbon nano-tube being compounded in this composite particles surface.
Preferably, described composite particles is micron order, such as 0.1 ~ 100 micron.
Preferably, in described composite cathode material for lithium ion cell, nano-silicon content is 20 ~ 70wt%, such as: 21wt%, 22wt%, 25wt%, 29wt%, 31wt%, 35wt%, 39wt%, 41wt%, 45wt%, 50wt%, 55wt%, 59wt%, 61wt%, 64wt%, 66wt%, 68wt%, 69wt% etc., more preferably 30 ~ 65wt%, is particularly preferably 40 ~ 60wt%.
Preferably, in described composite cathode material for lithium ion cell, lithium titanate content is 20 ~ 70wt%, such as: 21wt%, 22wt%, 24wt%, 26wt%, 29wt%, 31wt%, 35wt%, 40wt%, 45wt%, 49wt%, 51wt%, 59wt%, 61wt%, 64wt%, 66wt%, 68wt%, 69wt% etc., more preferably 25 ~ 60wt%, is particularly preferably 30 ~ 50wt%.
Preferably, in described composite cathode material for lithium ion cell, content of carbon nanotubes is 1 ~ 20wt%, such as: 1.1wt%, 1.2wt%, 1.5wt%, 2wt%, 2.9wt%, 3.1wt%, 3.5wt%, 4wt%, 6wt%, 8wt%, 11wt%, 14wt%, 16wt%, 18wt%, 19wt% etc., more preferably 3 ~ 15wt%, is particularly preferably 5 ~ 10wt%.
An object of the present invention is also the preparation method providing a kind of described composite cathode material for lithium ion cell, said method comprising the steps of:
(1) nano-silicon and lithium titanate are disperseed in a solvent, then carry out wet ball-milling, make lithium titanate clad nano silicon;
(2) carbon nano-tube is disperseed in a solvent;
(3) mixed liquor that slurry step (1) obtained and step (2) obtain mixes, and spray drying process, obtains lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
One of ordinary skill in the art should be appreciated that the order of step (1) and step (2) is interchangeable, do not affect effect of the present invention, and the technical scheme after step (1) and step (2) exchange sequence is still in protection scope of the present invention.
Preferably, described nano-silicon is spherical silicon.
Preferably, described nano-silicon particle diameter is 5 ~ 50 nanometers, such as: 6 nanometers, 8 nanometers, 9 nanometers, 11 nanometers, 15 nanometers, 19 nanometers, 21 nanometers, 25 nanometers, 29 nanometers, 31 nanometers, 35 nanometers, 39 nanometers, 41 nanometers, 45 nanometers, 48 nanometers, 49 nanometers etc., more preferably 10 ~ 40 nanometers, are particularly preferably 20 ~ 30 nanometers.
Preferably, described lithium titanate is powder.
Preferably, described lithium titanate particle diameter is 0.1 ~ 5 μm, such as: 0.11 μm, 0.12 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.7 μm, 0.9 μm, 1.4 μm, 1.6 μm, 2 μm, 2.5 μm, 2.9 μm, 3.1 μm, 3.6 μm, 4 μm, 4.5 μm, 4.8 μm, 4.9 μm etc., more preferably 0.5 ~ 3 μm, be particularly preferably 0.8 ~ 1.5 μm.
Preferably, ultrasonic disperse is separated into described in step (1).
Preferably, described in step (1), jitter time is at least 1 hour, such as: 1.1 hours, 1.2 hours, 1.5 hours, 1.9 hours, 2.1 hours, 2.5 hours, 2.9 hours, 3.1 hours, 3.5 hours, 4 hours, 6 hours, 10 hours, 15 hours, 20 hours, 23 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, 46 hours, 47 hours, 49 hours, 50 hours, 60 hours etc., preferably 2 ~ 48 hours, particularly preferably 3 ~ 24 hours.
Preferably, solvent described in step (1) is the combination of in water, ethanol, acetone, oxolane, benzene,toluene,xylene, dimethyl formamide a kind or at least 2 kinds, the typical but non-limiting example of described combination has: the combination of water and ethanol, the combination of ether and acetone, the combination of Benzene and Toluene, the combination of oxolane, Benzene and Toluene, the combination of toluene, dimethylbenzene and dimethyl formamide, the combination of benzene,toluene,xylene and dimethyl formamide, the combination etc. of ether, acetone, oxolane, Benzene and Toluene, particularly preferably water.
Preferably, described in step (1), rotational speed of ball-mill is 200 ~ 600 revs/min, more preferably 250 ~ 550 revs/min, is particularly preferably 300 ~ 500 revs/min.
Preferably, described in step (1), Ball-milling Time is at least 1 hour, such as: 1.1 hours, 1.2 hours, 1.4 hours, 1.6 hours, 1.9 hours, 2.1 hours, 3 hours, 5 hours, 10 hours, 14 hours, 16 hours, 18 hours, 19 hours, 21 hours, 25 hours, 30 hours etc., more preferably 1.5 ~ 20 hours, be particularly preferably 2 ~ 15 hours.
Preferably, ultrasonic disperse is separated into described in step (2).
Preferably, described in step (2), jitter time is at least 10 minutes, such as: 11 minutes, 12 minutes, 14 minutes, 16 minutes, 19 minutes, 21 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes, 59 minutes, 61 minutes, 70 minutes, 80 minutes, 95 minutes, 98 minutes, 99 minutes, 110 minutes, 120 minutes etc., more preferably 15 ~ 100 minutes, be particularly preferably 20 ~ 60 minutes.
Preferably, solvent described in step (2) is the combination of in water, ethanol, acetone, oxolane, benzene,toluene,xylene, dimethyl formamide a kind or at least 2 kinds, the typical but non-limiting example of described combination has: the combination of water and ethanol, the combination of ether and acetone, the combination of Benzene and Toluene, the combination of oxolane, Benzene and Toluene, the combination of toluene, dimethylbenzene and dimethyl formamide, the combination of benzene,toluene,xylene and dimethyl formamide, the combination etc. of ether, acetone, oxolane, Benzene and Toluene, particularly preferably water.
Preferably, step (1) is identical with step (2) described solvent kind.
Preferably, described spraying dry inlet temperature is 150 ~ 400 DEG C, more preferably 180 ~ 350 DEG C, is particularly preferably 200 ~ 300 DEG C.
Preferably, described spray drying exit temperature is 60 ~ 110 DEG C, more preferably 70 ~ 100 DEG C, is particularly preferably 75 ~ 95 DEG C.
Preferably, the preparation method of described composite cathode material for lithium ion cell, comprises the following steps:
(1) by nano-silicon and lithium titanate ultrasonic disperse in aqueous, then carry out wet ball-milling, make lithium titanate clad nano silicon;
(2) by carbon nano-tube ultrasonic disperse in aqueous;
(3) mixed liquor that slurry step (1) obtained and step (2) obtain mixes, and spraying dry, obtains lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
The present invention passes through mechanical means, nano-silicon, lithium titanate and carbon nano-tube are carried out compound, because lithium titanate has zero strain, in electrochemical reaction process, reduce electrolyte to greatest extent on the one hand to contact with the direct of silicon, thus control the embedding lithium degree of depth of silicon to a certain extent, on the other hand, lithium titanate stable structure can suppress the deformation degree of silicon.By spray drying process, carbon nano-tube is wrapped in the micron order composite particles surface of lithium titanate clad nano silicon, the conductance of material can be improved, improve its high-rate performance.By the Si/Li that the complex method of simple low consumption prepares 4ti 5o 12/ CNT ternary material, has played the advantage of often kind of material to greatest extent, reaches extraordinary effect.
Accompanying drawing explanation
Fig. 1 is Si/Li 4ti 5o 12the structural representation of/CNT composite material.
Reference numeral:
1-CNTs; 2-LTO(and Li 4ti 5o 12).
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
To be the ball shaped nano silicon of 20 nanometers and 2.5g particle diameter by 2g particle diameter the be lithium titanate powdery of 1.5 μm ultrasonic disperse 5 hours in the 50ml aqueous solution, transfer in ball grinder and carry out wet-milling, rotating speed 400 revs/min, ball milling 5 hours is to reach the object of the even clad nano silicon of lithium titanate.Another preparation 0.5g carbon nano-tube, abundant ultrasonic disperse 30 minutes in the 10ml aqueous solution.Slurry after ball milling is added in carbon nano-tube solution, then carries out high-speed stirred 1 hour.After through spraying dry (inlet temperature 250 DEG C, outlet temperature 80 DEG C), form a kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
Battery makes, electrochemical property test is as follows: Si/Li 4ti 5o 12/ CNT composite negative pole material, acetylene black and PVDF(Kynoar) mass ratio be 80:10:10, by Si/Li 4ti 5o 12/ CNT composite material and acetylene black mix, then PVDF(Kynoar is added) (PVDF is the PVDF/NMP solution of the 0.02g/mL prepared, NMP is 1-METHYLPYRROLIDONE) solution, be coated on Copper Foil, in 120 DEG C of vacuumizes 24 hours in vacuum drying chamber, cut-off footpath be the disk of 19 centimetres as work electrode, lithium metal is to electrode, electrolyte is LiPF6/EC-DMC-EMC(volume ratio 1:1:1), be assembled into two electrode simulated batteries being full of in Ar glove box.Charging/discharging voltage scope is 2.0 ~ 0.01V, and charging and discharging currents density is 100mA/g(0.5C).After tested, discharge capacity is 983mAh/g first, and efficiency for charge-discharge is 85.7%, and after 20 times, capability retention is 99.1%.
Embodiment 2
To be the ball shaped nano silicon of 30 nanometers and 1.7g particle diameter by 1.5g particle diameter the be lithium titanate powdery of 0.8 μm ultrasonic disperse 3 hours in the 35ml aqueous solution, transfer in ball grinder and carry out wet-milling, rotating speed 300 revs/min, ball milling 4 hours is to reach the object of the even clad nano silicon of lithium titanate.Another preparation 0.15g carbon nano-tube, abundant ultrasonic disperse 20 minutes in the 10ml aqueous solution.Slurry after ball milling is added in carbon nano-tube solution, then carries out high-speed stirred 1 hour.After through spraying dry (inlet temperature 200 DEG C, outlet temperature 75 DEG C), form a kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
The test of electrode preparation and property is identical with embodiment 1.After tested, discharge capacity is 989mAh/g first, and efficiency for charge-discharge is 86.1%, and after 20 times, capability retention is 99.0%.
Embodiment 3
To be the ball shaped nano silicon of 25 nanometers and 2.4g particle diameter by 3g particle diameter the be lithium titanate powdery of 1.0 μm ultrasonic disperse 6 hours in the 55ml aqueous solution, transfer in ball grinder and carry out wet-milling, rotating speed 500 revs/min, ball milling 6 hours is to reach the object of the even clad nano silicon of lithium titanate.Another preparation 1.3g carbon nano-tube, abundant ultrasonic disperse 30 minutes in the 30ml aqueous solution.Slurry after ball milling is added in carbon nano-tube solution, then carries out high-speed stirred 1 hour.After through spraying dry (inlet temperature 300 DEG C, outlet temperature 90 DEG C), form a kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
The test of electrode preparation and property is identical with embodiment 1.After tested, discharge capacity is 985mAh/g first, and efficiency for charge-discharge is 88.9%, and after 20 times, capability retention is 97.5%.
Embodiment 4
To be the ball shaped nano silicon of 5 nanometers and 1.25g particle diameter by 3.5g particle diameter the be lithium titanate powdery of 5.0 μm dispersed with stirring 48 hours in 60ml ethanol, transfer in ball grinder and carry out wet-milling, rotating speed 600 revs/min, ball milling 1 hour is to reach the object of the even clad nano silicon of lithium titanate.Another preparation 0.25g carbon nano-tube, abundant dispersed with stirring 100 minutes in 30ml ethanol.Slurry after ball milling is added in carbon nano-tube solution, then carries out high-speed stirred 2 hours.After through spraying dry (inlet temperature 400 DEG C, outlet temperature 110 DEG C), form a kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
The test of electrode preparation and property is identical with embodiment 1.After tested, discharge capacity is 976mAh/g first, and efficiency for charge-discharge is 82.3%, and after 20 times, capability retention is 93.5%.
Embodiment 5
To be the ball shaped nano silicon of 50 nanometers and 3.5g particle diameter by 1.0g particle diameter the be lithium titanate powdery of 0.1 μm ultrasonic disperse 1 hour in 80ml water, transfer in ball grinder and carry out wet-milling, rotating speed 200 revs/min, ball milling 20 hours is to reach the object of the even clad nano silicon of lithium titanate.Another preparation 0.5g carbon nano-tube, abundant ultrasonic disperse 10 minutes in 20ml water.Slurry after ball milling is added in carbon nano-tube solution, then carries out high-speed stirred 1 hour.After through spraying dry (inlet temperature 150 DEG C, outlet temperature 60 DEG C), form a kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
The test of electrode preparation and property is identical with embodiment 1.After tested, discharge capacity is 965mAh/g first, and efficiency for charge-discharge is 89.2%, and after 20 times, capability retention is 99.6%.
Embodiment 6
To be the ball shaped nano silicon of 40 nanometers and 1.0g particle diameter by 3.0g particle diameter the be lithium titanate powdery of 0.4 μm dispersed with stirring 48 hours in 60ml acetone, transfer in ball grinder and carry out carrying out wet-milling in ball milling, rotating speed 250 revs/min, ball milling 18 hours is to reach the object of the even clad nano silicon of lithium titanate.Another preparation 1.0g carbon nano-tube, abundant dispersed with stirring 100 minutes in 20ml acetone.Slurry after ball milling is added in carbon nano-tube solution, then carries out high-speed stirred 1 hour.After through spraying dry (inlet temperature 360 DEG C, outlet temperature 105 DEG C), form a kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
The test of electrode preparation and property is identical with embodiment 1.After tested, discharge capacity is 981mAh/g first, and efficiency for charge-discharge is 83.6%, and after 20 times, capability retention is 99.2%.
Embodiment 7
To be the ball shaped nano silicon of 10 nanometers and 2.45g particle diameter by 2.5g particle diameter the be lithium titanate powdery of 4 μm dispersed with stirring 36 hours in 70ml toluene, transfer in ball grinder and carry out wet-milling, rotating speed 550 revs/min, ball milling 1.5 hours is to reach the object of the even clad nano silicon of lithium titanate.Another preparation 1.0g carbon nano-tube, abundant dispersed with stirring 15 minutes in 20ml toluene.Slurry after ball milling is added in carbon nano-tube solution, then carries out high-speed stirred 1 hour.After through spraying dry (inlet temperature 180 DEG C, outlet temperature 75 DEG C), form a kind of lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
The test of electrode preparation and property is identical with embodiment 1.After tested, discharge capacity is 982mAh/g first, and efficiency for charge-discharge is 84.7%, and after 20 times, capability retention is 99.4%.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (42)

1. a composite cathode material for lithium ion cell, comprises the composite particles be made up of lithium titanate clad nano silicon and the carbon nano-tube being compounded in this composite particles surface;
Wherein, described composite particles is micron order;
In described composite cathode material for lithium ion cell, nano-silicon content is 20 ~ 70wt%;
In described composite cathode material for lithium ion cell, lithium titanate content is 20 ~ 70wt%;
In described composite cathode material for lithium ion cell, content of carbon nanotubes is 1 ~ 20wt%.
2. composite cathode material for lithium ion cell as claimed in claim 1, it is characterized in that, in described composite cathode material for lithium ion cell, nano-silicon content is 30 ~ 65wt%.
3. composite cathode material for lithium ion cell as claimed in claim 2, it is characterized in that, in described composite cathode material for lithium ion cell, nano-silicon content is 40 ~ 60wt%.
4. composite cathode material for lithium ion cell as claimed in claim 1, it is characterized in that, in described composite cathode material for lithium ion cell, lithium titanate content is 25 ~ 60wt%.
5. composite cathode material for lithium ion cell as claimed in claim 4, it is characterized in that, in described composite cathode material for lithium ion cell, lithium titanate content is 30 ~ 50wt%.
6. composite cathode material for lithium ion cell as claimed in claim 1, it is characterized in that, in described composite cathode material for lithium ion cell, content of carbon nanotubes is 3 ~ 15wt%.
7. composite cathode material for lithium ion cell as claimed in claim 6, it is characterized in that, in described composite cathode material for lithium ion cell, content of carbon nanotubes is 5 ~ 10wt%.
8. a preparation method for composite cathode material for lithium ion cell as claimed in claim 1, comprises the following steps:
(1) nano-silicon and lithium titanate are disperseed in a solvent, then carry out wet ball-milling, make lithium titanate clad nano silicon;
(2) carbon nano-tube is disperseed in a solvent;
(3) mixed liquor that slurry step (1) obtained and step (2) obtain mixes, and spraying dry, obtains lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
9. method as claimed in claim 8, it is characterized in that, described nano-silicon is spherical silicon.
10. method as claimed in claim 9, it is characterized in that, described nano-silicon particle diameter is 5 ~ 50 nanometers.
11. methods as claimed in claim 10, it is characterized in that, described nano-silicon particle diameter is 10 ~ 40 nanometers.
12. methods as claimed in claim 11, it is characterized in that, described nano-silicon particle diameter is 20 ~ 30 nanometers.
13. methods as claimed in claim 8, it is characterized in that, described lithium titanate is powder.
14. methods as claimed in claim 13, it is characterized in that, described lithium titanate particle diameter is 0.1 ~ 5 μm.
15. methods as claimed in claim 14, it is characterized in that, described lithium titanate particle diameter is 0.5 ~ 3 μm.
16. methods as claimed in claim 15, it is characterized in that, described lithium titanate particle diameter is 0.8 ~ 1.5 μm.
17. methods as claimed in claim 8, it is characterized in that, step is separated into ultrasonic disperse described in (1).
18. methods as claimed in claim 8, it is characterized in that, described in step (1), jitter time is at least 1 hour.
19. methods as claimed in claim 18, it is characterized in that, described jitter time is 2 ~ 48 hours.
20. methods as claimed in claim 19, it is characterized in that, described jitter time is 3 ~ 24 hours.
21. methods as claimed in claim 8, is characterized in that, solvent described in step (1) is the combination of in water, ethanol, acetone, oxolane, benzene,toluene,xylene, dimethyl formamide a kind or at least 2 kinds.
22. methods as claimed in claim 21, it is characterized in that, described solvent is water.
23. methods as claimed in claim 8, it is characterized in that, described in step (1), rotational speed of ball-mill is 200 ~ 600 revs/min.
24. methods as claimed in claim 23, it is characterized in that, described rotational speed of ball-mill is 250 ~ 550 revs/min.
25. methods as claimed in claim 24, it is characterized in that, described rotational speed of ball-mill is 300 ~ 500 revs/min.
26. methods as claimed in claim 8, it is characterized in that, described in step (1), Ball-milling Time is at least 1 hour.
27. methods as claimed in claim 26, it is characterized in that, described Ball-milling Time is 1.5 ~ 20 hours.
28. methods as claimed in claim 27, it is characterized in that, described Ball-milling Time is 2 ~ 15 hours.
29. methods as claimed in claim 8, it is characterized in that, step is separated into ultrasonic disperse described in (2).
30. methods as claimed in claim 8, it is characterized in that, described in step (2), jitter time is at least 10 minutes.
31. methods as claimed in claim 30, it is characterized in that, described jitter time is 15 ~ 100 minutes.
32. methods as claimed in claim 31, it is characterized in that, described jitter time is 20 ~ 60 minutes.
33. methods as claimed in claim 8, is characterized in that, solvent described in step (2) is the combination of in water, ethanol, acetone, oxolane, benzene,toluene,xylene, dimethyl formamide a kind or at least 2 kinds.
34. methods as claimed in claim 33, it is characterized in that, described solvent is water.
35. methods as claimed in claim 8, is characterized in that, step (1) is identical with step (2) described solvent kind.
36. methods as claimed in claim 8, it is characterized in that, described spraying dry inlet temperature is 150 ~ 400 DEG C.
37. methods as claimed in claim 36, it is characterized in that, described spraying dry inlet temperature is 180 ~ 350 DEG C.
38. methods as claimed in claim 37, it is characterized in that, described spraying dry inlet temperature is 200 ~ 300 DEG C.
39. methods as claimed in claim 8, it is characterized in that, described spray drying exit temperature is 60 ~ 110 DEG C.
40. methods as claimed in claim 39, it is characterized in that, described spray drying exit temperature is 70 ~ 100 DEG C.
41. methods as claimed in claim 40, it is characterized in that, described spray drying exit temperature is 75 ~ 95 DEG C.
42. methods as claimed in claim 8, is characterized in that, said method comprising the steps of:
(1) by nano-silicon and lithium titanate ultrasonic disperse in aqueous, then carry out wet ball-milling, make lithium titanate clad nano silicon;
(2) by carbon nano-tube ultrasonic disperse in aqueous;
(3) mixed liquor that slurry step (1) obtained and step (2) obtain mixes, and spraying dry, obtains lithium ion battery Si/Li 4ti 5o 12/ CNT composite negative pole material.
CN201210407835.XA 2012-10-23 2012-10-23 Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof Active CN102891306B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210407835.XA CN102891306B (en) 2012-10-23 2012-10-23 Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210407835.XA CN102891306B (en) 2012-10-23 2012-10-23 Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102891306A CN102891306A (en) 2013-01-23
CN102891306B true CN102891306B (en) 2015-04-01

Family

ID=47534752

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210407835.XA Active CN102891306B (en) 2012-10-23 2012-10-23 Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102891306B (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103326009B (en) * 2013-06-05 2015-08-19 深圳市斯诺实业发展有限公司 A kind of preparation method of high capacity lithium titanate anode material
CN103326010A (en) * 2013-06-05 2013-09-25 深圳市斯诺实业发展有限公司永丰县分公司 Process for preparing nano-silicon-doped composite-lithium-titanate anode materials
CN103682268B (en) * 2013-12-04 2016-01-20 上海纳米技术及应用国家工程研究中心有限公司 The preparation method of the silicium cathode material of a kind of carbon, lithium titanate double-coated
CN103700816B (en) * 2013-12-12 2016-02-03 天津巴莫科技股份有限公司 A kind of preparation method of lithium ion battery silicon based composite material
KR101900780B1 (en) * 2014-03-21 2018-09-20 중국 과학원, 쑤저우 나노기술 및 나노바이오닉스 연구소 Porous carbon nanotube microsphere and preparation method therefor and application thereof, lithium metal-skeleton carbon composite material and preparation method therefor, negative electrode, and battery
KR102161625B1 (en) * 2014-05-09 2020-10-05 삼성에스디아이 주식회사 Negative electrode, lithium battery including the same and method of manufacture of lithium battery
CN104681860B (en) * 2015-02-09 2017-03-01 惠州市豪鹏科技有限公司 A kind of can fast charging and discharging high-voltage lithium ion batteries and preparation method thereof
CN106159242A (en) * 2016-08-31 2016-11-23 中国电力科学研究院 A kind of core shell structure Si Li4ti5o12the preparation method of composite
CN106856240B (en) * 2017-01-06 2020-03-24 中昕（福建）石墨烯科技有限公司 Graphene power battery with excellent performance and preparation method thereof
KR102308723B1 (en) * 2017-10-19 2021-10-05 주식회사 엘지에너지솔루션 Negative electrode active material, negative electrode comprising the negative electrode active material, and lithium secondarty battery comprising the negative electrode
CN108365195A (en) * 2018-02-06 2018-08-03 深圳市普锐能源科技有限公司 A kind of lithium ion battery nucleocapsid negative material and preparation method thereof
CN110400914A (en) * 2018-04-25 2019-11-01 银隆新能源股份有限公司 A kind of silicon-carbon cathode material preparation method of lanthanium titanate lithium cladding
CN108695494A (en) * 2018-04-25 2018-10-23 福建翔丰华新能源材料有限公司 A kind of preparation method preparing lithium titanate cladding silicon-carbon composite cathode material
KR102364480B1 (en) * 2018-05-15 2022-02-18 주식회사 엘지에너지솔루션 Negative electrode active material, negative electrode comprising the negative electrode active material, and lithium secondarty battery comprising the negative electrode
CN111180663A (en) * 2018-11-13 2020-05-19 北方奥钛纳米技术有限公司 Negative electrode material and preparation method thereof, negative plate and lithium ion battery
CN109786665A (en) * 2018-12-20 2019-05-21 上海力信能源科技有限责任公司 A kind of silicon-carbon composite cathode pole piece and preparation method thereof
CN109752398A (en) * 2019-02-25 2019-05-14 广州能源检测研究院 A method of detection lithium titanate purity
CN110649246A (en) * 2019-10-05 2020-01-03 浙江理工大学 Lithium ion battery SiLiMn2O4Preparation method of CNT (carbon nanotube) composite positive electrode material
CN111081992B (en) * 2019-10-12 2021-10-12 开封大学 Preparation method of binder-free lithium ion battery negative electrode material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101630732A (en) * 2009-07-27 2010-01-20 深圳市德方纳米科技有限公司 Nanoscale lithium titanate compound and preparation method thereof
CN101841017A (en) * 2009-03-16 2010-09-22 中国科学院成都有机化学有限公司 Lithium titanate/carbon/carbon nano tube composite electrode material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5463652B2 (en) * 2008-11-14 2014-04-09 Ｔｄｋ株式会社 Active material and electrode manufacturing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101841017A (en) * 2009-03-16 2010-09-22 中国科学院成都有机化学有限公司 Lithium titanate/carbon/carbon nano tube composite electrode material and preparation method thereof
CN101630732A (en) * 2009-07-27 2010-01-20 深圳市德方纳米科技有限公司 Nanoscale lithium titanate compound and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Si/Li4Ti5O12复合锂离子电池负极材料的制备、结构和电化学性能;项良顺,王锭笙,高明霞,刘永锋,潘洪革;《材料科学与工程学报》;20110228;第29卷(第1期);第47-49页 *

Also Published As

Publication number Publication date
CN102891306A (en) 2013-01-23

Similar Documents

Publication Publication Date Title
CN102891306B (en) Lithium ion battery Si/Li4Ti5O12/CNT composite negative pole material and preparation method thereof
CN104617269B (en) A kind of silicon alloy composite negative pole material, preparation method and lithium ion battery
CN103441247B (en) A kind of high performance silicon/graphene oxide negative material constructed based on chemical bond and preparation method thereof
CN100492721C (en) Lithium ion battery pole piece with high multiplying power and production thereof
CN104009210B (en) A kind of porous silicon/carbon composite material, Preparation method and use
CN107170965B (en) Silicon-carbon composite material and preparation method and application thereof
CN109103399B (en) Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery
CN101950804B (en) Method for preparing spherical SnS2 anode material of lithium ion battery
CN105226285B (en) A kind of porous Si-C composite material and preparation method thereof
CN103236534B (en) A kind of preparation method of lithium ion battery silicon oxide/carbon composite negative pole material
CN105655592A (en) Silicon-based negative electrode of lithium ion battery and method for preparing silicon-based negative electrode of lithium ion battery
CN105932253B (en) SiO2@SnO2Clad structure ion cathode material lithium and its preparation method and application
CN102169985A (en) Preparation method of lithium ion battery carbon anode material with graphene-like structure
CN103515609B (en) THAQ/ graphene composite material, its preparation method, anode and lithium ion battery
CN102983317A (en) Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery
WO2017032166A1 (en) Preparation method for lithium battery negative-electrode slurry doped with tin powder
CN114335469B (en) Lithium ion battery anode material and preparation method thereof
CN105355875A (en) Tungsten oxide nanowire wound composite material, preparation method and application
CN111180701B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN104600296A (en) Preparation method of Se-C positive electrode composite material of lithium-selenium battery
CN101913556A (en) Preparation method of cobalt-silicon oxide/carbon nanocomposite
CN107732203A (en) A kind of preparation method of nano ceric oxide/graphene/sulphur composite
CN105742695A (en) Lithium-ion battery and preparation method thereof
CN107093711A (en) Monodispersed SiOxThe magnanimity preparation method of C complex microspheres
CN110336035B (en) Tin dioxide/aluminum oxide doped carbon composite material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20190612

Address after: 243000 No. 1669, North Section of Huolishan Avenue, Cihu High-tech Zone, Ma'anshan City, Anhui Province

Patentee after: Zhongke (Ma'anshan) New Material Science Park Co., Ltd.

Address before: 100190 No. 1 north of Zhongguancun, Haidian District, Haidian District, Beijing

Patentee before: Institute of Process Engineering, Chinese Academy of Sciences

TR01 Transfer of patent right