CN110459756A - Lithium ion battery supports the preparation of high density nanocomposite with three-dimensional porous carbon - Google Patents
Lithium ion battery supports the preparation of high density nanocomposite with three-dimensional porous carbon Download PDFInfo
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- CN110459756A CN110459756A CN201910751896.XA CN201910751896A CN110459756A CN 110459756 A CN110459756 A CN 110459756A CN 201910751896 A CN201910751896 A CN 201910751896A CN 110459756 A CN110459756 A CN 110459756A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims description 51
- 239000007791 liquid phase Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 239000011280 coal tar Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 19
- 230000002427 irreversible effect Effects 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 230000004087 circulation Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241001269238 Data Species 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to lithium ion battery equipment technical field, specially a kind of lithium ion battery supports the preparation of high density nanocomposite with three-dimensional porous carbon.It includes solution dispersion, carbon thermal reduction, drying steps that the three-dimensional porous carbon of lithium ion battery provided by the invention, which supports the preparation method of high density nanocomposite,.Lithium ion battery prepared by the present invention supports high density nanocomposite with three-dimensional porous carbon, it solves tin and is easy to polymerization balling-up at high temperature, since tin particles are larger, when tin is prepared into nano particle, contact of the carbon with tin is had certain problems, and when the content of tin is less, material irreversible capacity is limited, the problem of when the content of tin is larger, irreversible capacity is very big, but cycle performance is deteriorated.
Description
Technical field
The present invention relates to lithium ion battery equipment technical field, the three-dimensional porous carbon branch of specially a kind of lithium ion battery
Support the preparation of high density nanocomposite.
Background technique
Lithium ion battery is commercialized mechanism of new electrochemical power sources in 1991, compared with other batteries, has reversible charge and discharge
Capacity is high, recharge often, operating voltage is high and many excellent properties such as self discharge is small, in recent years, purposes is more next
It is wider, such as since mobile phone, laptop, digital camcorder, electric vehicle, especially oil crisis generation, electronic vapour
Vehicle is raised to practical application schedule, and lithium ion battery is since plurality of advantages is more applicable for power battery of electric motor car, together
When, this also puts forward new requirements the partial properties of lithium ion battery, such as it is highly-safe, can high current charge-discharge, urgently
The performance to lithium ion battery positive and negative electrode material used at present is needed to improve, or research and development are novel positive and negative
Material, at this stage, lithium ion battery negative material is based on graphitized carbon material, but carbon material is raw in discharge process for the first time
At SEI film, will cause irreversible capacity loss, also result in the variation and poor electric contact of carbon electrode internal structure sometimes；
It may cause battery failure because of the decomposition of protective layer when high temperature or cause safety issue；The unit bodies of graphite cathode simultaneously
Product capacity is relatively low, it is difficult to meet the requirement of such as cells in notebook computer, batteries of electric automobile high-energy density, lithium ion
The research and development progress of cell positive material is very fast, and LiMn2O4, the LiFePO4 being such as commercialized at this stage are being researched and developed
Nickelate, phosphate, silicate etc. propose the research and development of negative electrode material and faster therefore research and develop high capacity with higher requirement
Very urgent with the negative electrode material of high performance-price ratio, Fuji company researcher has found amorphous Sn-polymetallic orefield within 1997
(abbreviation TCO) shows preferable cycle life and higher reversible capacity for lithium ion battery negative material, this result
The extensive attention of people is caused after " Science " is delivered, it is considered to be very promising negative electrode material, the theory of metallic tin
Quality specific volume 994mAh/g is 2.67 times of graphite (372mAh/g), while being had and solvent intermiscibility is good, highly-safe, valence
The advantages that lattice are cheap, from a wealth of sources, due to tin volume expansion after lithium insertion, up to original 2-3 times, it is easy to lead to glass putty
Change, lithium can not be deviate from from material, cause efficiency for charge-discharge to decline, while cycle performance declines, this is that the material needs to solve
Critical issue.
Studies have shown that volume change is obviously reduced in alloying process when the crystalline size of Sn is reduced to Nano grade,
When Sn crystalline size is reduced to 80nm or less, volume change can be ignored, so if can prepare a nanometer Sn/ for Sn crystalline substance
C composite, can solve tin-based material be difficult to commercial applications service life is short and two high hang-ups of irreversible capacity, it is numerous
Researcher use prepare tin oxide, tin alloy, tin nano thin-film and the methods of tin and other materials are compound with keep its
Stable structure, guarantee cycle performance, tin and its composite material have greatly as negative electrode of lithium ion battery during charge and discharge
Development potentiality, for it due to the expansion issues after lithium insertion, numerous researchers have done a large amount of effort to promote its quotient
Industry process, but all exist or this or that deficiency: tin alloy cycle performance is still undesirable, and the content of tin is reduced to very low amount
When have preferable cycle performance, but capacity only has the 1/3 of graphite, loses application value；The oxide of tin is due to irreversible capacity
Higher, there are application difficults；Tin thin film material has high specific capacity and good cycle life, and specific discharge capacity can be up to
600-900mAh/g, but since it can only be prepared into single nano thin-film, volume and capacity ratio is too low, can not be applied to practical
Battery can be only applied to hull cell in other words；Tin/carbon composite there are two types of preparation method, one is with carbon coating in tin
On, high temperature carbon thermal reduction is prepared into composite material, and since tin is easy to polymerization balling-up at high temperature, tin particles are larger, when tin system
When at nano particle, contact of the carbon with tin is had certain problems；Another method is on the carbon of tin cladding, when containing for tin
When measuring less, the material is with good performance, and when the content of tin is larger, irreversible capacity is very big, and cycle performance is deteriorated, because
This, needs to carry out more in-depth study to tin and its composite material, to obtain composite material not only with height ratio capacity, but also tool
There is the high circulation service life, highdensity composite material establishes solid foundation for the practical application of the material, therefore needs a kind of lithium
Ion battery supports the preparation of high density nanocomposite to solve the above problems with three-dimensional porous carbon.
Summary of the invention
In order to solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of three-dimensional porous carbon of lithium ion battery
Support the preparation of high density nanocomposite.Lithium ion battery prepared by the present invention supports high density nanometer with three-dimensional porous carbon
Composite material solves tin and is easy to polymerization balling-up at high temperature, since tin particles are larger, when tin is prepared into nano particle,
Contact of the carbon with tin has certain problems, and when the content of tin is less, material irreversible capacity is limited, when the content of tin
The problem of when larger, irreversible capacity is very big, but cycle performance is deteriorated.
To achieve the above object, technical scheme is as follows:
A kind of preparation method of lithium ion battery three-dimensional porous carbon support high density nanocomposite, including walk as follows
It is rapid:
Step S1, solution dispersion is carried out: by medium temperature coal tar and SnCl2As raw material, liquid is added with mass ratio 15-30:1
In phase medium, 5-10min is stirred by ultrasonic, obtains liquid phase dispersion liquid；
Step S2, it carries out carbon thermal reduction: distilling flask is added in the liquid phase dispersion liquid obtained by step A and covers sealing
Plug, then heats cucurbit, carries out reduction reaction 2-4h in 300-400 DEG C of addition reducing agent, obtains Sn/C composite wood
Material；
Step S3, Sn/C composite material acetone washing 3-5 times for preparing step S2, be freeze-dried 12-24h to get.
Further, liquid phase medium is organic amine aqueous solution in the step S1.
Further, reducing agent is sodium sulfite in the step S2.
Further, Sn/C composite material made from the step S2 is that bulk density is greater than 2.91g/cm3High density
Stereoscopic three-dimensional structure.
Further, Sn/C composite material made from the step S2 is volume capacity density 1455-3360mAh/cm3's
High density stereoscopic three-dimensional structure.
Further, the size of tin is less than 80nm in Sn/C composite material made from the step S2, and the tin is solid
Nano thin-film or nano bar-shape.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) present invention is first by the basis of forefathers prepare nanometer tin thin-film material with good chemical property
Secondary proposition prepares a kind of preparation method of the Sn/C composite material of high density stereoscopic three-dimensional structure, and this method makes tin with three-dimensional nanometer
The form of film and nanometer rods is present in porous carbon, forms good composite construction, solves tin and is easy to gather at high temperature
Ball is synthesized, tin particles are larger, when tin is prepared into nano particle, the problem of carbon and tin cannot be contacted preferably.
(2) provided by the invention to be put forward for the first time with highdensity Sn/C composite material, its high energy storage lithium mechanism is carried out
Research, the material have 2.91g/cm3Above bulk density has 1455-3360mAh/cm3Volume capacity density so that
Not only there is height ratio capacity using the battery of the material, but also there is the high circulation service life, have a good application prospect.
Detailed description of the invention
Fig. 1 is the structure that the lithium ion battery provided of the invention supports high density nanocomposite with three-dimensional porous carbon
Schematic diagram；
Fig. 2 is the TEM that the lithium ion battery provided of the invention supports high density nanocomposite with three-dimensional porous carbon
Figure；
Fig. 3 is the circulation that the lithium ion battery provided of the invention supports high density nanocomposite with three-dimensional porous carbon
Performance curve schematic diagram.
Specific embodiment
The specific embodiment of form by the following examples makees further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment.
Embodiment 1, a kind of lithium ion battery support high density nanocomposite with three-dimensional porous carbon
The lithium ion battery supports the preparation method of high density nanocomposite with three-dimensional porous carbon, including walks as follows
It is rapid:
Step S1, solution dispersion is carried out: by medium temperature coal tar and SnCl2As raw material, liquid phase is added with mass ratio 15:1
In medium, 5min is stirred by ultrasonic, obtains liquid phase dispersion liquid；
Step S2, it carries out carbon thermal reduction: distilling flask is added in the liquid phase dispersion liquid obtained by step A and covers sealing
Plug, then heats cucurbit, carries out reduction reaction 2h progress in 300 DEG C of addition sodium sulfites, obtains Sn/C composite wood
Material；
Step S3, Sn/C composite material acetone washing 3 times for preparing step S2, be freeze-dried 12h to get.
Liquid phase medium is organic amine aqueous solution in the step S1.
Sn/C composite material made from the step S2 is bulk density 2.91g/cm3High density stereoscopic three-dimensional structure.
Sn/C composite material made from the step S2 is volume capacity density 1455mAh/cm3High density stereoscopic three-dimensional
Structure.
The size of tin is 30nm in Sn/C composite material made from the step S2, and the tin is three-dimensional nano thin-film.
Embodiment 2, a kind of lithium ion battery support high density nanocomposite with three-dimensional porous carbon
The lithium ion battery supports the preparation method of high density nanocomposite with three-dimensional porous carbon, including walks as follows
It is rapid:
Step S1, solution dispersion is carried out: by medium temperature coal tar and SnCl2As raw material, liquid phase is added with mass ratio 23:1
In medium, 10min is stirred by ultrasonic, obtains liquid phase dispersion liquid；
Step S2, it carries out carbon thermal reduction: distilling flask is added in the liquid phase dispersion liquid obtained by step A and covers sealing
Plug, then heats cucurbit, carries out reduction reaction 3h in 320 DEG C of addition sodium sulfites, obtains Sn/C composite material；
Step S3, Sn/C composite material acetone washing 5 times for preparing step S2, be freeze-dried 8h to get.
Liquid phase medium is organic amine aqueous solution in the step S1.
It is 10.62g/cm that Sn/C composite material made from the step S2, which is bulk density,3High density stereoscopic three-dimensional knot
Structure.
Sn/C composite material made from the step S2 is volume capacity density 3080mAh/cm3High density stereoscopic three-dimensional
Structure.
The size of tin is 65nm in Sn/C composite material made from the step S2, and the tin is nano bar-shape.
Embodiment 3, a kind of lithium ion battery support high density nanocomposite with three-dimensional porous carbon
The lithium ion battery supports the preparation method of high density nanocomposite with three-dimensional porous carbon, including walks as follows
It is rapid:
Step S1, solution dispersion is carried out: by medium temperature coal tar and SnCl2As raw material, liquid phase is added with mass ratio 30:1
In medium, 10min is stirred by ultrasonic, obtains liquid phase dispersion liquid；
Step S2, it carries out carbon thermal reduction: distilling flask is added in the liquid phase dispersion liquid obtained by step A and covers sealing
Plug, then heats cucurbit, carries out reduction reaction 4h in 400 DEG C of addition reducing agents, obtains Sn/C composite material；
Step S3, Sn/C composite material acetone washing 5 times for preparing step S2, freeze-drying for 24 hours to get.
Liquid phase medium is organic amine aqueous solution in the step S1.
It is 7.28g/cm that Sn/C composite material made from the step S2, which is bulk density,3High density stereoscopic three-dimensional knot
Structure.
Sn/C composite material made from the step S2 is volume capacity density 3360mAh/cm3High density stereoscopic three-dimensional
Structure.
The size of tin is 70nm in Sn/C composite material made from the step S2, and the tin is three-dimensional nano thin-film.It is right
Ratio 1, a kind of lithium ion battery composite material
The preparation method of the lithium ion battery composite material, includes the following steps:
Step S1, solution dispersion is carried out: by medium temperature coal tar and SnCl2As raw material, liquid phase is added with mass ratio 10:1
In medium, 10min is stirred by ultrasonic, obtains liquid phase dispersion liquid；
Step S2, it carries out carbon thermal reduction: distilling flask is added in the liquid phase dispersion liquid obtained by step A and covers sealing
Plug, then heats cucurbit, carries out reduction reaction 3h in 320 DEG C of addition sodium sulfites, obtains Sn/C composite material；
Step S3, Sn/C composite material acetone washing 5 times for preparing step S2, be freeze-dried 8h to get.
Liquid phase medium is organic amine aqueous solution in the step S1.
It is 1.56g/cm that Sn/C composite material made from the step S2, which is bulk density,3Stereoscopic three-dimensional structure.
Sn/C composite material made from the step S2 is volume capacity density 2438mAh/cm3Stereoscopic three-dimensional structure.
The size of tin is 65nm in Sn/C composite material made from the step S2, and the tin is nano bar-shape.
Comparative example 1 is substantially the same manner as Example 3, and difference is, medium temperature coal tar and SnCl2Mass ratio become 10:1.
Comparative example 2, a kind of lithium ion battery composite material
The preparation method of the lithium ion battery composite material, includes the following steps:
Step S1, solution dispersion is carried out: by medium temperature coal tar and SnCl2It is added in liquid phase medium as raw material, ultrasound is stirred
10min is mixed, liquid phase dispersion liquid is obtained；
Step S2, it carries out carbon thermal reduction: distillation burning is added in the liquid phase dispersion liquid obtained by step A and covers sealing-plug,
Then cucurbit is heated, carries out reduction reaction 3h in 320 DEG C of addition sodium borohydrides, obtains Sn/C composite material；
Step S3, Sn/C composite material acetone washing 5 times for preparing step S2, be freeze-dried 8h to get.
Liquid phase medium is organic amine aqueous solution in the step S1.
Sn/C composite material made from the step S2 is bulk density 1.22g/cm3High density stereoscopic three-dimensional structure.
Sn/C composite material made from the step S2 is volume capacity density 1820mAh/cm3High density stereoscopic three-dimensional
Structure.
The size of tin is 65nm in Sn/C composite material made from the step S2, and the tin is nano bar-shape.
Comparative example 2 is substantially the same manner as Example 3, and difference is, reducing agent is changed to sodium borohydride in comparative example 2.
45 DEG C of test example one, battery cycle performance tests
Respectively using the composite material of embodiment 1-3 and comparative example 1-2 preparation as negative electrode material, with anode by collector aluminium
Foil and lithium ion battery is prepared coated in the positive-material lithium manganate layer composition on plus plate current-collecting body, is denoted as embodiment 4-6 respectively
With comparative example 3-4.
Test method: at 45 DEG C, by test material with 1C constant-current charge to 4.40V, then constant-voltage charge to electric current is
0.05C, then with 1C constant-current discharge to 3.0V, such charge/discharge, calculate separately circulating battery 50 times, 100 times, 300 times and
Capacity retention ratio after 500 times.
Test result: 45 DEG C of cycle performance test results of battery are shown in Table 1.
Capacity retention ratio (%)=n-th circulation discharge capacity/discharge capacity for the first time after lithium ion battery n times circulation
× 100%.
Table 1 battery, 45 DEG C of cycle performance test datas
As shown in Table 1, the capacity retention ratio after lithium ion battery 500 times circulations of embodiment 4-6 preparation is held in
75.5% or more, 1.0C and 2.0C multiplying power discharge capacity than lithium that 90.2% and 84.9%, wherein prepared by embodiment 5 from
Sub- battery performance is best, is highly preferred embodiment of the present invention, in contrast, lithium ion battery 500 times of comparative example 3-4 preparation are followed
Capacity retention ratio after ring is respectively less than 62.1%, 1.0C and 2.0C multiplying power discharge capacity ratio is respectively smaller than 79.8% He
70.2%, performance is poor, and test result shows that lithium ion battery provided by the invention supports high density nanometer with three-dimensional porous carbon
The lithium ion battery specific capacity of composite material preparation is improved, and has good cyclical stability.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (6)
1. the preparation method that a kind of lithium ion battery supports high density nanocomposite with three-dimensional porous carbon, which is characterized in that
Include the following steps:
Step S1, solution dispersion is carried out: by medium temperature coal tar and SnCl2As raw material, liquid phase is added with mass ratio 15-30:1 and is situated between
In matter, 5-10min is stirred by ultrasonic, obtains liquid phase dispersion liquid；
Step S2, it carries out carbon thermal reduction: distilling flask is added in the liquid phase dispersion liquid obtained by step A and covers sealing-plug, so
Cucurbit is heated afterwards, reduction reaction 2-4h is carried out in 300-400 DEG C of addition reducing agent, obtains Sn/C composite material；
Step S3, Sn/C composite material acetone washing 3-5 times for preparing step S2, be freeze-dried 12-24h to get.
2. the preparation side that lithium ion battery as described in claim 1 supports high density nanocomposite with three-dimensional porous carbon
Method, which is characterized in that liquid phase medium is organic amine aqueous solution in the step S1.
3. the preparation side that lithium ion battery as described in claim 1 supports high density nanocomposite with three-dimensional porous carbon
Method, which is characterized in that reducing agent is sodium sulfite in the step S2.
4. the preparation side that lithium ion battery as described in claim 1 supports high density nanocomposite with three-dimensional porous carbon
Method, which is characterized in that Sn/C composite material made from the step S2 is that bulk density is greater than 2.91g/cm3High density it is three-dimensional
Three-dimensional structure.
5. the preparation side that lithium ion battery as described in claim 1 supports high density nanocomposite with three-dimensional porous carbon
Method, which is characterized in that Sn/C composite material made from the step S2 is volume capacity density 1455-3360mAh/cm3Height
Density stereoscopic three-dimensional structure.
6. the preparation side that lithium ion battery as described in claim 1 supports high density nanocomposite with three-dimensional porous carbon
Method, which is characterized in that the size of tin is less than 80nm in Sn/C composite material made from the step S2, and the tin is three-dimensional nanometer
Film or nano bar-shape.
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| CN101740783A (en) * | 2009-11-24 | 2010-06-16 | 太原理工大学 | Method for preparing fuel-cell catalyst carrier |
| CN102832374A (en) * | 2012-09-18 | 2012-12-19 | 奇瑞汽车股份有限公司 | Tin-carbon composite material, preparation method thereof and lithium-ion battery |
| CN104300151A (en) * | 2014-10-13 | 2015-01-21 | 同济大学 | Preparation method of porous carbon ball-loaded M-Sn alloy nano particle composite material |
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| CN101740783A (en) * | 2009-11-24 | 2010-06-16 | 太原理工大学 | Method for preparing fuel-cell catalyst carrier |
| CN102832374A (en) * | 2012-09-18 | 2012-12-19 | 奇瑞汽车股份有限公司 | Tin-carbon composite material, preparation method thereof and lithium-ion battery |
| CN104300151A (en) * | 2014-10-13 | 2015-01-21 | 同济大学 | Preparation method of porous carbon ball-loaded M-Sn alloy nano particle composite material |
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