CN1812167A - Preperative method for nano tin dioxide doped compound carbide negative electrode material and lithium battery - Google Patents
Preperative method for nano tin dioxide doped compound carbide negative electrode material and lithium battery Download PDFInfo
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- CN1812167A CN1812167A CNA2005100328765A CN200510032876A CN1812167A CN 1812167 A CN1812167 A CN 1812167A CN A2005100328765 A CNA2005100328765 A CN A2005100328765A CN 200510032876 A CN200510032876 A CN 200510032876A CN 1812167 A CN1812167 A CN 1812167A
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- Y02E60/10—Energy storage using batteries
Abstract
This invention relates to a kind of producing method of high-capacity security nanometer tin dioxide material mixing with lithium ionic cell composite cathode material. The method combines heat treatment and ball-milling method together. It provides a kind of lithium cell using carbon composite material as cathode. The said carbon composite material is produced according to this method. It can get security well lithium ionic cell cathode material with high lithium storing capacity. This nanometer doped composite cathode material increases cell specific energy and high-power discharging ability greatly when the said material is used in liquid lithium ionic cell and especially in polymer lithium ionic cell. It improves cell security.
Description
Affiliated technical field:
The present invention relates to preparation method and a kind of lithium battery of the lithium battery composite carbon negative polar material of doping nano-tin dioxide.
Prior art
Along with the high speed development of World Economics, for alleviating the energy crisis of following with it and reducing environmental pollution, people thirst for the electrical source of power of certain high-energy chemistry power supply as motor vehicle, boats and ships always.The universal people of making of the appearance of lithium ion battery and mobile communication equipment are heightened to the confidence that lithium ion battery is developed into electrical source of power.Entered since the new century, power-type lithium ion battery has become the focus of electrochemistry and field of chemical power source research and development.
Lithium ion battery is as a kind of state-of-the art chemical power source system, it have the operating voltage height (3.6～3.7V), light weight, specific energy height, have extended cycle life (＞1000 week), temperature range (20～50 ℃) that storge quality is good, broad, comparatively safe many outstanding advantages such as reliable, lithium ion battery is widely used in mobile communication and notebook computer.Development electric vehicle high capacity lithium ion battery can satisfy the requirements at the higher level of electric motor car to battery, promotes the battery of electric vehicle upgrading, has profound significance, and therefore lithium ion battery is a strong candidate in the competition of following battery of electric vehicle.
Lithium ion battery has good comprehensive performances, in portable electric appts such as mobile phone, obtained using widely, but lithium ion battery is simply amplified the manufacturing electrokinetic cell be used for electric automobile, then bring serious safety issue, restricted its use in electric automobile and other field.Therefore more there is immeasurable market in research and development big capacity lithium dynamical battery truly in fields such as power car, UPS electrokinetic cell, military affairs, space flight and aviation.
The negative material that present commercialization lithium ion battery is adopted is material with carbon element, mainly is graphite intercalation compound, and its reversible capacity is lower, surpasses classical graphite and inserts compound L iC
6Theoretical reversible capacity 372mAh/g.And, LiC
6Being a kind of energy-rich compound, having very high reactivity with moisture content, also intense reaction can take place under the situation of bump, is lithium ion battery is deposited safety problem as electrical source of power one of the main reasons.
Summary of the invention
Purpose of the present invention proposes a kind of preparation method of the high-capacity secure nano tin dioxide material doped lithium ion battery composite negative pole material that heat treatment and ball grinding method are combined.A kind of lithium battery that adopts this material as cathode is provided simultaneously.Can obtain lithium storage content height, the good lithium ion battery negative material of fail safe with this method, the specific energy and the high power discharge performance of this kind mixed nanometer composite negative pole material application in liquid lithium ionic cell especially polymer Li-ion battery obviously raising battery, and effectively improved the security performance of battery.
The preparation method of high-capacity secure nano-stannic oxide doped lithium ion battery composite carbon negative polar material of the present invention comprises following each step:
1). get certain amount of nano tin ash emulsion, join in the material with carbon element, the solid-liquid weight ratio of nano-stannic oxide emulsion is 10%～20%, the weight ratio of nano-stannic oxide emulsion and material with carbon element is 30%～60%, with mixture dispersed with stirring in closed container, rotating speed is 1500～2000rpm, and the time is 1～2h.
2). the prepared material of step 1) is placed ultrasonic disperser, handle 10～30min.
3). with step 2) prepared material is in 50～80 ℃ of oven dry, the time is 212h.
4). in 400～600 ℃ of calcinings, heat treatment time is 4～10h with the prepared material of step 3).
5). the prepared material of step 4) is carried out ball-milling treatment in ball-grinding machine, the time is 2～8h.
A kind of lithium battery is characterized in that: cathode of lithium battery comprises the composite carbon negative polar material of the nanometer titanium dioxide tin dope of said method making.Cathode of lithium battery includes material with carbon element, conductive carbon black and the binding agent of nanometer titanium dioxide tin dope, the optimization composition of its negative pole and content following (weight portion):
100 parts of nano-stannic oxide doped compound carbide negative electrode materials
0～15 part of conductive carbon black
1～10 part of binding agent
50～100 parts of solvents
The present invention contrasts prior art and has following advantage: the present invention adopts above-mentioned nano combined carbon negative pole material to have higher lithium storage content, and the lithium ion battery of using this negative material has higher specific energy, good high power discharge ability and security performance.
Description of drawings:
Fig. 1 is the structure chart of coiled lithium ion battery;
Fig. 2 is the structure chart of stack type lithium ion battery;
Fig. 3 is the charging and discharging curve of embodiment 5;
Fig. 4 is the multiplying power electricity curve of embodiment 5;
Fig. 5 is the curve that overcharges of embodiment 5;
Specific embodiment
Embodiment 1:
With the solid-liquid weight ratio is that 15% nano-stannic oxide emulsion and D50 are the material with carbon element (CMS of 5 μ m, Shanghai Shanshan Science and Technology Co., Ltd's manufacturing) mixture dispersed with stirring in closed container, the weight ratio of nano-stannic oxide emulsion and material with carbon element is 30%, stirs 1h with the 1500rpm rotating speed.After in ultrasonic disperser, handling 10min, in 60 ℃ of about 8h of baking.Then, the material of gained in 500 ℃ of calcining 8h, and is handled 6h at ball-grinding machine.
Embodiment 2:
Preparation manipulation and embodiment 1 with, just the weight ratio of nano-stannic oxide emulsion and material with carbon element being changed into is 45%.
Embodiment 3:
Preparation manipulation and embodiment 1 with, just the weight ratio of nano-stannic oxide emulsion and material with carbon element being changed into is 60%.
Comparative example 1:
Preparation manipulation and embodiment 1 are that negative electrode active material directly adopts the CMS material with carbon element together.
Embodiment 4:
Cathode of lithium battery adopts material with carbon element, conductive carbon black (chemical plant, Fujian), the binding agent (PVdF761 with the nanometer titanium dioxide tin dope in the embodiment of the invention 1, U.S. ATOFINA company) and solvent (NMP, Jin Long chemical plant, Nanjing), it is formed and content following (weight portion):
100 parts of nano-stannic oxide doped and compounded material with carbon elements
Conductive carbon black 0-10 part
Binding agent 1-10 part
50～100 parts of solvents
The positive electrode of lithium battery adopts lithium cobalt oxygen (Guizhou new material development Co., Ltd), conductive carbon black, binding agent and solvent, and it is formed and content following (weight portion):
100 parts of positive electrodes
0～15 part of conductive carbon black
1～10 part of binding agent
50～100 parts of solvents
Adopt above-mentioned material to make the both positive and negative polarity of lithium battery respectively, battery structure is consulted as shown in Figure 1, and electrolyte is selected LiPF for use
6+ EC: EMC: DMC (1: 1: 1) is that housing material is made into lithium ion battery with box hat or aluminum plastic film.
The major parameter and the performance of battery are as follows:
LiCoO
2: NMC=2: 1 (weight ratio)
Anodal thickness: 0.18mm (comprising the collector aluminium foil)
Negative pole thickness: 0.20mm (comprising copper foil of affluxion body)
Charging cut-ff voltage: 4.2V
Discharge cut-off voltage: 2.75V
Charging current: 5A
Discharging current: 5A
Multiplying power discharging: 1ItA (10A), 2ItA (20A), 3ItA (30A), 4ItA (40A)
Overcharge current: 0.3A
Battery capacity: 10Ah
Embodiment 5:
Preparation manipulation and embodiment 4 adopt embodiment 2 described material negative poles together.
Embodiment 6:
Preparation manipulation and embodiment 4 adopt embodiment 3 described material negative poles together.
Comparative example 2:
Preparation manipulation and embodiment 4 adopt comparative example 1 described negative plate together.
The experimental data of all embodiment is as shown in table 1.
Table 1 embodiment battery testing data
| Weight/g | 0.5ItA capacity/Ah | Specific energy/Wh.kg -1 | The 1ItA capacity *1 /％ | 2ItA capacity/% | 3ItA capacity/% | 4ItA capacity/% | The overcharging resisting ability *2 | ||
| The box hat structure | Embodiment 4 | 302 | 11.52 | 141 | 92.1 | 91.8 | 91.1 | 86.5 | 189 minutes, 5.35 |
| Embodiment | |||||||||
| 5 | 302 | 10.89 | 133 | 91.2 | 91.0 | 89.2 | 83.1 | 180 minutes, 5.22V | |
| Embodiment 6 | 305 | 10.23 | 124 | 90.6 | 90.3 | 88.6 | 82.3 | 160 minutes, 5.15V | |
| Comparative example 1 | 317 | 9.80 | 114 | 86.2 | 86.0 | 84.1 | 75.2 | 119 minutes, 4.96V | |
| The plastic-aluminum flexible packing structure | Embodiment 4 | 258 | 11.45 | 164 | 92.0 | 91.6 | 89.7 | 81.8 | 169 minutes, 5.30 |
| Embodiment | |||||||||
| 5 | 260 | 10.69 | 152 | 91.0 | 90.7 | 88.8 | 80.6 | 160 minutes, 5.25V | |
| Embodiment 6 | 260 | 10.10 | 143 | 90.2 | 90.0 | 88.6 | 80.5 | 158 minutes, 5.15V | |
| Comparative example 1 | 268 | 9.68 | 134 | 86.0 | 85.6 | 81.0 | 70.4 | Cell expansion, not blast | |
*1: the multiplying power output capacity is meant under this multiplying power condition, the percentage of the shared 0.5ItA output capacity of battery output capacity.
*2: the overcharging resisting ability is meant with 0.330.5ItA spends voltage, the time that is charged to battery and blasts.
By in the table as seen, adopt the nano-stannic oxide doped compound carbide negative electrode material after, box hat encapsulation lithium ion battery has all had than the raising of spoke degree greatly with specific energy, high rate performance and the security performance of polyalcohol flexible packing lithium ion battery.The CMS carbon negative pole material is obtained better doping vario-property effect, obtains best modified effect when the weight ratio of nano-stannic oxide emulsion and material with carbon element is 30%.
Principle of the present invention is by the activity site on the carbon base body nano-stannic oxide particle to be connected on the carbon matrix material, thereby the nano-stannic oxide particle is fixed, and constitute a spatial network thus, have a large amount of storage lithium activity sites, thereby improved the storage lithium capacity of carbon bulk material.
The less carbon matrix material of average grain diameter has reasonable space structure, its particle diameter and surface area all relatively are fit to the generation of nano-stannic oxide particle in the keyed jointing reaction of carbon base body surface, in the process of overcharging, also suppressed the formation of dendrite lithium accordingly, thereby having modified effect preferably, the specific energy of battery and overcharging resisting ability all increase.
The reason that MCMB obtains better modified effect be because of its surface state different with electrographite.
Graphite is layer structure, and the crystallite surface has end face (indentation), two kinds of different structures of basal plane (being the handrail shape), and end face has better reactivity, and its laciniation more helps the carrying out of nano-stannic oxide particle keyed jointing reaction.And basal plane activity is lower comparatively speaking, this has influenced the capacity and the multiplying power fan-out capability of battery to a certain extent.
MCMB is the space radial structure, and microsphere surface has many active holes, thereby MCMB can carry out the keyed jointing reaction of nano-stannic oxide from space three-dimensional structure, forms more complete spatial network than graphite.Thereby, adopt the nano-stannic oxide composite carbon negative polar material of MCMB modification to have higher storage lithium capacity, and the MCMB of particle diameter of the same race have better overcharging resisting ability than graphite under the situation of overcharging.Because, effectively improved the overcharging resisting ability of battery even the three-dimensional effect of MCMB has stoped the electro-deposition of lithium under the two-forty condition and the formation of dendrite lithium.
Adopt the polymer Li-ion battery of flexible package to have better comprehensive performance.The flexible package very light in weight has improved the specific energy of battery.Because this kind battery does not have the restriction of rigidity shell, its interface contact performance slightly is worse than lithium ion battery, thereby this internal resistance of cell is relatively large, and high rate performance is also corresponding will to be hanged down.But, the battery of this kind structure is in the process of overcharging, the side reaction that takes place in the battery under the situation even overcharge has produced a large amount of gas, on the one hand owing to adopted mixed nanometer tin ash composite carbon negative polar material to suppress the generation of gas to a certain extent, on the other hand because the flexible package plastic material has higher ductility, though bigger dilatancy takes place battery, also having cushioned interior pressure simultaneously sharply increases, and has suppressed the generation of inside battery thermal runaway reaction.Then, along with the reduction gradually of the activity of active material in the battery, the inside battery temperature rise progressively descends, and final cell integrated losing activity avoided the generation of blast.
Claims (4)
1, a kind of preparation method of nano-stannic oxide doped compound carbide negative electrode material is characterized in that may further comprise the steps:
1), gets certain amount of nano tin ash emulsion, join in the graphite, the solid-liquid weight ratio of nano-stannic oxide emulsion is 10%～20%, the weight ratio of nano-stannic oxide emulsion and graphite is 30%～60%, with mixture dispersed with stirring in closed container, rotating speed is 1500～2000rpm, and the time is 1～2h;
2), the prepared material of step (1) is placed ultrasonic disperser, processing 20min;
3), with the prepared material of step (2) in 50～80 ℃ of oven dry, the time is 2～12h;
4), with the prepared material of step (3) in 500～800 ℃ of calcinings, heat treatment time is 4～10h;
5), the prepared material of step (4) is carried out ball-milling treatment in ball-grinding machine, the time is 2～8h.
2, the preparation method of nano-stannic oxide doped compound carbide negative electrode material according to claim 1 is characterized in that: the weight ratio of described nano-stannic oxide emulsion and graphite is 30%～45%.
3, a kind of lithium battery according to claim 1, it is characterized in that: cathode of lithium battery comprises the composite carbon negative polar material of nanometer titanium dioxide tin dope.
4, lithium battery according to claim 3 is characterized in that: described battery cathode comprises following component and proportioning (weight portion):
100 parts of the material with carbon elements of nanometer titanium dioxide tin dope
0～15 part of conductive carbon black
1～10 part of binding agent
50～100 parts of solvents.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082262A (en) * | 2010-12-31 | 2011-06-01 | 上海交通大学 | Method for preparing nano-carbon coated lithium battery anode material |
| CN105140488A (en) * | 2015-09-21 | 2015-12-09 | 江苏津谊新能源科技有限公司 | Anode material for lithium batteries |
| CN108321376A (en) * | 2018-02-08 | 2018-07-24 | 合肥工业大学 | A kind of N doping porous carbon nanofiber@tin dioxide lithium ion battery negative pole materials and preparation method thereof |
| CN106025343B (en) * | 2016-06-30 | 2018-10-02 | 深圳市德力普电池科技有限公司 | A kind of preparation method of negative electrode of lithium ion battery porous oxidation tin material |
| CN111485246A (en) * | 2020-04-17 | 2020-08-04 | 浙江长兴绿色电池科技有限公司 | In-situ electrolysis preparation method of carbon-based-metal oxide composite material |
-
2005
- 2005-01-26 CN CNA2005100328765A patent/CN1812167A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082262A (en) * | 2010-12-31 | 2011-06-01 | 上海交通大学 | Method for preparing nano-carbon coated lithium battery anode material |
| CN102082262B (en) * | 2010-12-31 | 2013-01-09 | 上海交通大学 | Method for preparing nano-carbon coated lithium battery anode material |
| CN105140488A (en) * | 2015-09-21 | 2015-12-09 | 江苏津谊新能源科技有限公司 | Anode material for lithium batteries |
| CN106025343B (en) * | 2016-06-30 | 2018-10-02 | 深圳市德力普电池科技有限公司 | A kind of preparation method of negative electrode of lithium ion battery porous oxidation tin material |
| CN108321376A (en) * | 2018-02-08 | 2018-07-24 | 合肥工业大学 | A kind of N doping porous carbon nanofiber@tin dioxide lithium ion battery negative pole materials and preparation method thereof |
| CN108321376B (en) * | 2018-02-08 | 2020-05-22 | 合肥工业大学 | N-doped porous carbon nanofiber @ tin dioxide lithium ion battery cathode material and preparation method thereof |
| CN111485246A (en) * | 2020-04-17 | 2020-08-04 | 浙江长兴绿色电池科技有限公司 | In-situ electrolysis preparation method of carbon-based-metal oxide composite material |
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