CN102195032A - Method for preparing pole piece of lithium ion battery - Google Patents
Method for preparing pole piece of lithium ion battery Download PDFInfo
- Publication number
- CN102195032A CN102195032A CN2010105913126A CN201010591312A CN102195032A CN 102195032 A CN102195032 A CN 102195032A CN 2010105913126 A CN2010105913126 A CN 2010105913126A CN 201010591312 A CN201010591312 A CN 201010591312A CN 102195032 A CN102195032 A CN 102195032A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- tube
- lithium ion
- slurry
- ion battery
- 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.)
- Granted
Links
Images
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a pole piece of a lithium ion battery. The method comprises the following steps of: adding carbon nano tube conductive agent powder into a solvent and a surfactant, and dispersing uniformly to obtain improved uniformly dispersed carbon nano tube slurry; preparing pole piece slurry by using the carbon nano tube slurry; and preparing the pole piece of the lithium ion battery by using the obtained pole piece slurry. Compared with the prior art, the method has the advantages that: the carbon nano tube is effectively dispersed into a cathode/anode material of the battery by using a surface dispersing agent, so the excellent performance of the carbon nano tube conductive agent can be exerted fully and the chemical performance of the lithium ion battery is enhanced greatly, namely 1) the inner resistance of the battery is reduced, the multiplying power performance and the energy density of the battery are improved, and specifically the large multiplying power charging and discharging performance is greatly improved; 2) the high/low temperature performance of the battery is improved and the application field of the lithium ion battery is expanded; 3) the cycle service life of the battery is prolonged; and 4) the safety performance of the battery is improved.
Description
Technical field
The present invention relates to a kind of method for preparing lithium ion battery pole pieces, relate in particular to the application process of a kind of carbon nanotube conducting agent on the preparation electrodes of lithium-ion batteries.
Background technology
Lithium ion battery is owing to have that energy density height, operating voltage height, temperature limit are wide, advantage such as have extended cycle life, and be widely used as the power supply of various mobile devices, even in fields such as Aeronautics and Astronautics, navigation, automobile, Medical Devices, progressively replace other conventional batteries.
For battery, big its energy that influences of internal resistance is exported, and in use the interior voltage of battery itself is higher, and the voltage platform that can cause exporting reduces, thereby battery capacity is on the low side.This capacity is on the low side except outside the Pass having with the structure of battery, positive and negative pole material collocation, electrolyte system etc., also with anodal and negative material in addition, the interpolation kind of conductive carbon relevant with technology.In addition, the Conversion of energy that battery itself consumes in the discharge process is a heat energy, internal resistance greatly to battery exert oneself, battery life and fail safe all have considerable influence.Through research, the generation position of the internal resistance of cell comprises positive plate, negative plate, barrier film, external packing etc., and wherein positive plate is because the conductivity of material itself is low, and the ratio that its resistance accounts for internal resistance reaches 80-90%.
In addition, the application of current battery, especially lithium ion battery enlarges, and with regard to its use, is progressing into low temperature place in one's power, some high-temperature fields, and this just needs battery to have given play to better electrochemical performance under harsh conditions.Studies show that the relation of the high temperature performance of lithium ion battery and electrolyte, positive electrode, negative material is very big, especially the electric conductivity of positive electrode is very big to the battery performance influence under low temperature environment.
Moreover, another deficiency of lithium ion battery existence at present is to use the life-span shorter, the general use after 3～5 years just can not normally discharge and recharge, the disappearance of this function mainly is because a part of active material has lost the ability that stores lithium ion in the battery system, causes lithium ion normally not shuttle between both positive and negative polarity.Experiment shows, the electric conductivity that can be by improving positive and negative pole material and the structure of conductive agent prolong the useful life of battery.
Based on above analysis as seen, the electric conductivity of positive and negative pole material is the key that overcomes above-mentioned defective.In view of the above, the inventor think have certain draw ratio, the carbon nanotube conducting agent of electric conductivity excellence is that the ideal that addresses the above problem is selected.
Carbon nano-tube in 1991 by Japanese scientist's Sumio Iijima find (Helical microtubules ofgraphitic carbon "; S Iijima; Narure.Vol.354; P56 (1991)); because it has excellent mechanics; calorifics and electric property, caused scientific worker's concern, about its preparation, the report of sign and application performance is very many, application in lithium ion battery and field of batteries also has corresponding document, the equality people of kingdom as the Chinese Academy of Sciences joins (" carbon nano-tube is as the lithium ion cell positive conductive agent " in the positive pole with carbon nano-tube as electric conducting material, kingdom is flat, Chinese nanometer technology was used seminar, P302 (2004) in 2004), still, the internal resistance of above-mentioned lithium ion battery is still bigger, so that charge-discharge performance is not good.
Summary of the invention
The objective of the invention is to: provide a kind of method for preparing lithium ion battery pole pieces, with the stronger electrodes of lithium-ion batteries of preparation electric conductivity.
In order to realize the foregoing invention purpose, the present inventor is through the discovery of concentrating on studies for a long time, the carbon nano-tube of electric conductivity excellence reason as the electric conducting material poor effect in battery pole piece is to disperse not good enough, because for other common conductive carbon, carbon nano-tube is linear structure, diameter is littler, length is shorter, disperse to get up the easier agglomeration that occurs, therefore, the dispersion of carbon nano-tube is its major issue of using in battery.For this reason, proposed the carbon nano-tube powder added and carried out pre-dispersedly in solvent and the surfactant, the method that is prepared into slurry solves the difficulties in dispersion problem of conductive nano carbon.
The invention provides a kind of method for preparing lithium ion battery pole pieces, the steps include: to obtain the carbon nano-tube slurry being uniformly dispersed in carbon nano-tube powder adding solvent and the surfactant; With carbon nano-tube pulp preparation pole piece slurry, and the pole piece pulp preparation electrodes of lithium-ion batteries to obtain.
Because carbon nano-tube is thin more, its specific area is big more, oil factor is high more, thereby need more bonding agent, on the other hand, the particle diameter of both positive and negative polarity active material is between several μ m to 20 μ m at present, therefore in order to reach better dispersion and electric action, as a kind of improvement of method for preparing lithium ion battery pole pieces of the present invention, described carbon nano-tube is single wall, double-walled or multi-walled carbon nano-tubes, and its diameter is that 2-20nm, length are 0.2-20 μ m.
As a kind of improvement of method for preparing lithium ion battery pole pieces of the present invention, in the described carbon nano-tube slurry, the weight content of carbon nano-tube is 2-13.8%.
A kind of improvement as method for preparing lithium ion battery pole pieces of the present invention, described surfactant is the surfactant of stable in properties in lithium ion battery battery chemical work voltage range, is in dispersant, defoamer, wetting agent, the levelling agent one or more.
A kind of improvement as method for preparing lithium ion battery pole pieces of the present invention, described carbon nano-tube slurry comprises that aqueous slurry and oil are slurry: at aqueous slurry, described dispersant is polyoxyethylene ether block copolymers, polyamine salt, alcohols etc., as AFE1080, PE100; At oil is in the slurry, and described dispersant is polysiloxanes and modifier thereof, polyamine salt, organic solvent (high molecular weight alkane, ester class, ketone etc.), polypyrrole alkane ketone (PVP) etc., as Texaphor 963, PVP.
As a kind of improvement of method for preparing lithium ion battery pole pieces of the present invention, described defoamer is polysiloxanes or its modifier, as 8034,8034A, E8, E2.
As a kind of improvement of method for preparing lithium ion battery pole pieces of the present invention, described wetting agent is for polyethenoxy alkylphenols, as 436,478.
As a kind of improvement of method for preparing lithium ion battery pole pieces of the present invention, described levelling agent is polysilanes solvent (ester class, an alcohols etc.), as 878,876.
A kind of improvement as method for preparing lithium ion battery pole pieces of the present invention, described pole piece is positive plate or negative plate, and employed positive electrode active materials is one or more in cobalt acid lithium, lithium nickelate, lithium nickel cobalt multicomponent material, LiFePO4, the lithium manganese phosphate in the positive plate; Employed negative active core-shell material is one or more in graphite, lithium titanate, silicon-carbon alloy, the silicon stannum alloy in the negative plate.
Described carbon nanotube conducting agent has different additions to different active materials, by preparation just/solid part weight of cathode size, the addition of carbon nano-tube is: when negative active core-shell material was graphite, carbon nano-tube was 0.1-3.0%; When negative active core-shell material was lithium titanate, carbon nano-tube was 0.5-5.0%; When positive electrode active materials was cobalt acid lithium, carbon nano-tube was 0.2-5.0%; When positive electrode active materials was lithium nickelate, carbon nano-tube was 0.2-6.0%; When positive electrode active materials was lithium nickel cobalt multicomponent material, carbon nano-tube was 1.0-6.0%; When positive electrode active materials was LiFePO4, carbon nano-tube was 1.0-6.0%; When positive electrode active materials was lithium manganese phosphate, carbon nano-tube was 1.0-7.0%.
Described solvent is one or more in deionized water, alcohols (as ethanol, ethylene glycol, isopropyl alcohol) or the ketone (as acetone, cyclohexanone, N-methyl pyrrolidone etc.).
Catalyst metals impurity content, the especially iron introduced during made of carbon nanotubes, metals content impurities such as nickel are lower than 1% by the requirement of dry state weight.
Described aqueous slurry comprises aqueous solvent, surfactant and carbon nanotube conducting agent, and described aqueous solvent is at least a in deionized water, the isopropyl alcohol; Described oil is pulp bales oil scraper solvent, surfactant and carbon nanotube conducting agent, and described oil-based solvent is one or more in N-methyl pyrrolidone (NMP), cyclohexanone, acetone, the isopropyl alcohol.
Described battery is rectangular cell or cylindrical battery.
With respect to prior art, the present invention utilizes surface dispersant that carbon nano-tube is scattered in the battery plus-negative plate material effectively, thereby the excellent properties of carbon nano-tube is not fully exerted, significantly promoted the following chemical property of lithium ion battery: 1) reduced the internal resistance of battery, the battery high rate performance and the energy density that have promoted, especially the high rate charge-discharge performance significantly improves; 2) improve the high temperature performance of battery, widened the application of lithium ion battery; 3) prolonged life-span that recycles of battery; 4) improved the security performance of battery.
Description of drawings
Below in conjunction with the drawings and specific embodiments, the present invention and useful technique effect thereof are elaborated, wherein:
Fig. 1 and Fig. 2 be the preparation of each embodiment and Comparative Examples just/negative plate SEM figure.
Embodiment
Carbon nanotube conducting agent used in the present invention is that a class can be added the good conductive material that is applied in anode, the negative pole, it is the electron conduction that is used for improving pole piece as electric conducting material on the one hand, be to improve the internal heat dissipating of battery on the other hand, thereby promote the performance of battery comprehensively as the linear composition that a class has an excellent heat conductivity performance.The diameter of carbon nano-tube used in the present invention is 2-20nm, and length is 0.2-20 μ m, can be single wall, double-walled or multi-walled carbon nano-tubes.
Below will progressively be described in the preparation process of using the lithium ion battery of carbon nanotube conducting agent in the both positive and negative polarity.
Agents useful for same and supplier (source and the composition of all ingredients that table 1 is just adopted when illustrating that the present invention tests, do not represent the reagent that adopts other similar reagent or other suppliers to provide just can not realize the present invention) as shown in table 1 in this specification.
Table 1 embodiment agents useful for same and supplier's detail
| The material sequence number | Reagent name | Supplier |
| 1 | The agent of carbon conductive nano | Dongguan New Energy Technology Co |
| 2 | Graphite | Dongguan New Energy Technology Co |
| 3 | Cobalt acid lithium | Dongguan New Energy Technology Co |
| 4 | Lithium nickel cobalt manganese | Dongguan New Energy Technology Co |
| 5 | LiFePO4 | Dongguan New Energy Technology Co |
| 6 | Lithium manganese phosphate | Dongguan New Energy Technology Co |
| 7 | Aluminosilicate alloy material | Dongguan New Energy Technology Co |
| 8 | Super“p”Li | Te Migao company |
| 9 | Kynoar | Sol dimension chemical industry Co., Ltd |
| 10 | Styrene-butadiene latex | Dongguan New Energy Technology Co |
| 11 | Surfactant | Ninghua worker Co., Ltd of section |
| 12 | N-methyl pyrrolidone (NMP) | Dongguan New Energy Technology Co |
| 13 | PVDF-HEP(PVDF) | Sol dimensional polymers company |
| 14 | Electrolyte | Dongguan New Energy Technology Co |
| 15 | Sodium carboxymethylcellulose | Dongguan New Energy Technology Co |
1, carbon nano-tube pulp preparation
It is slurry or aqueous slurry that the carbon nano-tube slurry can be made oil, below its preparation process will be described respectively.
1. oil is that the preparation process of slurry is generally in the prior art: take by weighing the NMP of 95～98 weight portions and other solvent in dispersion cup, the carbon nanotube conducting agent that adds 2～5 weight portions again mixes and is uniformly dispersed, and adopts or does not adopt sand mill and three-roller to grind.Below to be called the carbon nano-tube oil of prior art be slurry to the slurry that will herein prepare.
2. oil of the present invention is that the pulp preparation process is: the solvent that takes by weighing 85～95 weight portions is in dispersion cup, the dispersant that adds 0.2～1.0 weight portion more respectively, 0.05 the defoamer of～0.2 weight portion, 0.1 the wetting agent of～1.0 weight portions, 0.1 the levelling agent of～1.0 weight portions, after treating that all surface activating agent fully is uniformly dispersed, the carbon nanotube conducting agent that in solution, adds 2.0～13.8 weight portions while stirring, reinforced finish and be uniformly dispersed after obtain slurry, above-mentioned slurry is pumped into again and be ground to suitable granularity in sand mill or the three-roller, below to be called carbon nano-tube oil of the present invention be slurry to the slurry that will herein prepare.
Table 2 is several specific embodiment component tables of slurry for carbon nano-tube oil.
Table 2, carbon nano-tube oil are slurry embodiment component table (weight portion)
3. the preparation process of aqueous slurry is generally in the prior art: the deionized water that takes by weighing 95～98 weight portions is in dispersion cup, the carbon nanotube conducting agent that adds 2～5 weight portions again disperses to stir, and re-uses or do not use sand mill or three-roller to grind.Below the slurry that will herein prepare is called the carbon nano-tube aqueous slurry of prior art.
4. aqueous slurry preparation process of the present invention is: the water solvent that takes by weighing 90～95 weight portions is in dispersion cup, the dispersant that adds 0.1～1.0 weight portion more respectively, 0.1 the defoamer of～1.0 weight portions, 0.3 the wetting agent of～1.0 weight portions, 0.2 the levelling agent of～1.0 weight portions, after treating that surfactant fully is uniformly dispersed, the carbon nanotube conducting agent that in solution, adds 3.3～9.2 weight portions while stirring, reinforced finish and fully be uniformly dispersed again after obtain slurry, above-mentioned slurry is pumped into again and be ground to suitable granularity in sand mill or the three-roller, below the slurry that will herein prepare is called carbon nano-tube aqueous slurry of the present invention.
Table 3 is several specific embodiment component tables of carbon nano-tube aqueous slurry.
Table 3, carbon nano-tube aqueous slurry embodiment component table (weight portion)
2, the preparation of anode sizing agent
The preparation process of anode sizing agent is: the solvent that takes by weighing 5～60 weight portions is in dispersion cup, the adhesive that takes by weighing 0.7～3.9 weight portion again is uniformly dispersed in solvent, the carbon nano-tube slurry that adds 1.8～66.5 weight portions then, it is even to continue dispersed with stirring, the active material dispersed with stirring that adds 11.1～73.3 parts again is even, finally is prepared into the anode sizing agent sample of viscosity 2000～10000mPas.Comparative example's feed way and dispersing technology are identical with inventive embodiments.The embodiment component table of the anode sizing agent of the carbon nano-tube pulp preparation that makes among the use embodiment 1-1 to 1-6 is as shown in table 4.
The embodiment component table and the performance index of table 4, anode sizing agent
3, the preparation of cathode size
Cathode size is because different mining oily system and two kinds of carbon nano-tube slurries of water system of material:
1. the preparation process of water system cathode size is: the deionized water that takes by weighing 5.8～48.4 weight portions is in dispersion cup, add the carbon nano-tube aqueous slurry of 1.0～40.0 weight portions then and be uniformly dispersed, the effective active matter that adds 34.8～60.9 weight portions more also fully is uniformly dispersed, add the adhesive of 2.3～4.2 weight portions such as butadiene-styrene rubber etc. again and further be uniformly dispersed, finally be prepared into the cathode size of 1500～4000mPas.
2. oil is that the cathode size preparation process is: the solvent that takes by weighing 5.8～48.8 parts earlier is in dispersion cup, take by weighing adhesive fully dissolving in container of 2.3～4.8 parts again, the carbon nano-tube slurry that adds 3.3～40.0 weight portions more fully disperses in above-mentioned slurry, the effective active matter that adds 34.8～60.9 weight portions continues to be uniformly dispersed, and the qualified cathode size of finally preparing viscosity 2000～5000mPas is standby.
The embodiment component table of the cathode size of the carbon nano-tube pulp preparation that makes among the use embodiment 1-1 to 1-12 is as shown in table 5.
The embodiment component of table 5, cathode size and size performance index
4, cell preparation
With above-mentioned qualified anode and cathode slurry by the requirement of design Model (as 383450 square batteries, 423482 square batteries, 18650 cylindrical batteries etc.) on coating machine, coat qualified just/cathode pole piece.
Model by design is rolled and is assembled into battery with the just qualified/cathode pole piece of above-mentioned comparative sample and invention application examples, and the perfusion electrolyte carries out chemical membrane, wearing out makes lithium ion battery, detects the chemical property of battery, and with EIS pole piece resistance is carried out performance evaluation.
5, beneficial effect experiment
Above-mentioned battery is carried out high temperature storage, press UL 1642 standard detection battery safeties.
By UL 1642 standards battery is carried out high temperature performance and detect, and the chemical property of battery is assessed.
1, dispersion effect estimates one
One of difficulty that carbon nano-tube is used is a scattering problem, and especially dispersion is more difficult in water-based slurry, even the scattered slurry that is up to the standards still can be reunited together in storage process mutually.In order to detect dispersion effect of the present invention, the pole piece that utilizes above-mentioned all embodiment slurries to make is carried out SEM before rolling detect, obtain electromicroscopic photograph as shown in Figure 1 and Figure 2, as seen, the carbon nano-tube of contrast groups system is disperseed bad, tangible carbon nano-tube coarse granule occurred, and particle is the distribution of isolating, illustrates that there is big problem in the dispersion of carbon nano-tube.In the pole piece after improvement of the present invention and the PROCESS FOR TREATMENT, even carbon nanotube is distributed in the active material surface, and be interconnected to network-like each other, so just solved the problem of carbon nano-tube difficulties in dispersion, and no matter still in solvent-based system, all disperse finely, help the performance of conductive carbon material performance like this at aqueous based systems.
2, dispersion effect estimates two
The slurry of embodiment 2-1 to 2-20 and embodiment 3-1 to 3-14 is coated with the pole piece that makes, be rolled into the pole piece of different densities by different active materials, it is 10mm with 1000Hz～1Hz frequency test contact area that the pole piece after will preparing again adopts electrochemical impedance spectroscopy (EIS)
2Membrane resistance, obtain result as shown in table 6.
The membrane resistance measurement result that all embodiment of table 6 make
| Embodiment | Pole piece | Density (g/cm3) | Electric current (μ A) | ?1000Hz?Imp(mΩ) | Remarks |
| Embodiment 2-1 | Anodal | 3.90 | 13.677 | 32505.6 | The contrast sample |
| Embodiment 2-2 | Anodal | 3.90 | -25.389 | 45758.9 | The contrast sample |
| Embodiment 2-3 | Anodal | 3.90 | -27.275 | 2928.8 | The invention application examples |
| Embodiment 2-4 | Anodal | 3.90 | 3.1693 | 2942.0 | The invention application examples |
| Embodiment 2-5 | Anodal | 3.30 | 3.1893 | 19708.8 | The contrast sample |
| Embodiment 2-6 | Anodal | 3.30 | 243.85 | 14853.0 | The contrast sample |
| Embodiment 2-7 | Anodal | 3.30 | -18.465 | 6058.0 | The invention application examples |
| Embodiment 2-8 | Anodal | 3.30 | -10.523 | 6817.5 | The invention application examples |
| Embodiment 2-9 | Anodal | 3.00 | 53.201 | 14853.0 | The contrast sample |
| Embodiment 2-10 | Anodal | 3.00 | -15.565 | 13058.0 | The contrast sample |
| Embodiment 2-11 | Anodal | 3.00 | -12.535 | 1817.5 | The invention application examples |
| Embodiment 2-12 | Anodal | 3.00 | 24.213 | 2025.5 | The invention application examples |
| Embodiment 2-13 | Anodal | 2.20 | -10.523 | 31986 | The contrast sample |
| Embodiment 2-14 | Anodal | 2.20 | -33.254 | 31868 | The contrast sample |
| Embodiment 2-15 | Anodal | 2.20 | -23.586 | 9111 | The invention application examples |
| Embodiment 2-16 | Anodal | 2.20 | -35.546 | 9565 | The invention application examples |
| Embodiment 2-17 | Anodal | 2.00 | -10.523 | 184270 | The contrast sample |
| Embodiment 2-18 | Anodal | 2.00 | -15.368 | 181160 | The contrast sample |
| Embodiment 2-19 | Anodal | 2.00 | 22.306 | 7927 | The invention application examples |
| Embodiment 2-20 | Anodal | 2.00 | 57.568 | 7969 | The invention application examples |
| Embodiment 3-1 | Negative pole | 1.60 | 0.1342 | 6827 | The contrast sample |
| Embodiment 3-2 | Negative pole | 1.60 | 0.1869 | 6210 | The contrast sample |
| Embodiment 3-3 | Negative pole | 1.60 | 1.2342 | 4613 | The invention application examples |
| Embodiment 3-4 | Negative pole | 1.60 | 1.8612 | 2042 | The invention application examples |
| Embodiment 3-5 | Negative pole | 1.60 | 0.7642 | 3566 | The contrast sample |
| Embodiment 3-6 | Negative pole | 1.60 | 0.4375 | 2693 | Inventive embodiments |
| Embodiment 3-7 | Negative pole | 1.80 | 0.1316 | 14566.3 | The contrast sample |
| Embodiment 3-8 | Negative pole | 1.80 | -16.423 | 13338.5 | The contrast sample |
| Embodiment 3-9 | Negative pole | 1.80 | -16.258 | 8128.3 | The invention application examples |
| Embodiment 3-10 | Negative pole | 1.80 | -8.762 | 8377.2 | The invention application examples |
| Embodiment 3-11 | Negative pole | 1.40 | -8.586 | 14566.9 | The contrast sample |
| Embodiment 3-12 | Negative pole | 1.40 | 3.7523 | 17289.3 | The contrast sample |
| Embodiment 3-13 | Negative pole | 1.40 | 3.1569 | 8059 | The invention application examples |
| Embodiment 3-14 | Negative pole | 1.40 | 3.5823 | 11657 | The invention application examples |
By table 6 as seen, under the situation of same coating weight and identical compacted density, pole piece for the allovitalism material preparation, used process for dispersing of the present invention that carbon nano-tube is carried out pre-dispersed pole piece because electric conducting material and active material are uniformly dispersed, all there is distribution preferably in carbon nano-tube on three-dimensional, thereby its pairing membrane resistance obviously reduces, and helps improving the chemical property of battery.
3, to the influence of the big multiplying power discharging property of battery
To being assembled into the electric core of different structure respectively according to contrast groups and improvement group, and the battery of preparation is carried out chemical ageing and aging,, obtain performance data as shown in table 7 it being carried out the high rate performance test with the pole piece of each embodiment.
Discharge performance under the electric core different multiplying that table 7, each embodiment make
By table 7 as seen, used process for dispersing of the present invention that carbon nano-tube is carried out pre-dispersed electric core because carbon nano-tube is disperseed more evenly, the especially big multiplying power discharging property of the high rate performance of battery is significantly improved, and the benefit of bringing like this is can prepare high performance lithium ion battery to satisfy the instructions for use of large power supply such as electric energy storage station, electric tool, electric automobile etc.; On the other hand, when the use field of battery is less demanding, adds a spot of carbon nano-tube and can reach the result of use that the conductive carbon of more amount can reach, thereby promote the integral energy density of battery.
4, to the influence of battery high temperature performance
The high low temperature test result of the battery that table 8, each embodiment make
By table 8 as seen, compare with normal group, the low temperature of battery and high-temperature behavior are using process for dispersing of the present invention carbon nano-tube to be carried out all obtained raising in various degree after pre-dispersed, this might be after carbon nano-tube joins in the pole piece, because comparing with normal conductive carbon, carbon nano-tube has more stable electronic conductivity under high temperature and low temperature, thereby improved conduction and the heat conductivility of pole piece on three-dimensional, so just widened the scope of application of lithium ion battery, the former field that to use lithium ion battery under the specific condition of serving, also can give play to comparatively stable performance, thereby lithium ion battery can be applied in these new fields by using the battery that adds carbon nano-tube.
5, to the influence of cycle performance of battery
Cycle performance test result under table 9, the normal temperature
| Embodiment | Electricity core kind | Circulation ratio | Cycle-index | Capability retention |
| Embodiment 2-1 (contrast groups) | 383450 | 0.7C/0.5C | 338 | 64％ |
| Embodiment 2-3 (invention set of applications) | 383450 | 0.7C/0.5C | 746 | 88％ |
| Embodiment 2-5 (contrast groups) | 454261 | 0.5C/0.5C | 817 | 87％ |
| Embodiment 2-8 (invention set of applications) | 454261 | 0.5C/0.5C | 1445 | 66％ |
| Embodiment 3-1 (contrast groups) | 374270 | 0.7C/0.5C | 620 | 63％ |
| Embodiment 3-3 (invention set of applications) | 374270 | 0.7C/0.5C | 5000 | 93％ |
Table 10,45 degree are the cycle performance test result down
| Embodiment | Electricity core kind | Circulation ratio | Cycle-index | Capability retention |
| Embodiment 2-1 (contrast groups) | 383450 | 0.7C/0.5C | 500 | 72％ |
| Embodiment 2-3 (invention set of applications) | 383450 | 0.7C/0.5C | 500 | 74％ |
| Embodiment 2-5 (contrast groups) | 454261 | 0.5C/0.5C | 539 | 89％ |
| Embodiment 2-8 (invention set of applications) | 454261 | 0.5C/0.5C | 600 | 76％ |
| Embodiment 3-1 (contrast groups) | 374270 | 0.7C/0.5C | 799 | 82％ |
| Embodiment 3-3 (invention set of applications) | 374270 | 0.7C/0.5C | 732 | 93％ |
| Embodiment 3-7 (contrast groups) | 454261 | 0.5C/0.5C | 400 | 82％ |
| Embodiment 3-8 (invention set of applications) | 454261 | 0.5C/0.5C | 2200 | 89％ |
Table 11,60 degree are the cycle performance test result down
| Embodiment | Electricity core kind | Circulation ratio | Cycle-index | Capability retention |
| Embodiment 2-1 (contrast groups) | 383450 | 0.7C/0.5C | 652 | 68％ |
| Embodiment 2-3 (invention set of applications) | 383450 | 0.7C/0.5C | 720 | 70％ |
| Embodiment 2-5 (contrast groups) | 454261 | 0.5C/0.5C | 255 | 78％ |
| Embodiment 2-8 (invention set of applications) | 454261 | 0.5C/0.5C | 550 | 70％ |
| Embodiment 3-1 (contrast groups) | 374270 | 0.7C/0.5C | 912 | 79％ |
| Embodiment 3-4 (invention set of applications) | 374270 | 0.7C/0.5C | 1700 | 78％ |
| Embodiment 3-11 (contrast groups) | 18650 | 0.5C/0.5C | 400 | 59％ |
| Embodiment 3-13 (invention set of applications) | 18650 | 0.5C/0.5C | 6830 | 85％ |
Table 9 to table 11 has been listed each embodiment battery at normal temperature, cycle performance test result under 45 degree and 60 degree, compare with the contrast sample, having used process for dispersing of the present invention that carbon nano-tube is carried out pre-dispersed battery recycles the life-span lifting of matter has been arranged: common lithium-cobalt system battery cycle life can reach more than 1000 times, the battery of LiFePO4 system can reach more than 6000 times, be equivalent to the standard of common batteries use more than 5 years by 300 circulations, then this type of battery used 15～20 years, its chemical property is still very excellent, so just can save natural resources, alleviate environmental pollution, lithium ion battery can be used as permanent power station simultaneously, frontiers such as on-vehicle battery.
6, to the influence of battery safety
By UL 1642 standards the battery that each embodiment prepares has been carried out the test of secure context, the result is as shown in table 13.
The electrochemistry security performance of table 12, each embodiment battery
By table 12 as seen, compare with the battery of normal contrast groups, use process for dispersing of the present invention that carbon nano-tube is carried out pre-dispersed battery and had identical security performance, the performance of some projects is more excellent than normal group, this might be that there is heat release rapidly in inside battery under abuse condition, and the linear structure of carbon conductive nano agent and heat conductivility preferably, can be timely the local heat that produces in the battery be in time led away, thereby avoid situation about more worsening to occur as extreme cases such as blast, on fire, flatulence leakages.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (9)
1. a method for preparing lithium ion battery pole pieces is characterized in that, may further comprise the steps: with being uniformly dispersed in carbon nanotube conducting agent powder adding solvent and the surfactant, obtain uniform and stable dispersed carbon nano tube slurry; With carbon nano-tube pulp preparation pole piece slurry, and the pole piece pulp preparation electrodes of lithium-ion batteries to obtain.
2. method for preparing lithium ion battery pole pieces according to claim 1 is characterized in that: carbon nano-tube is that length is that 0.2-20 μ m, diameter are single wall, double-walled or the multi-walled carbon nano-tubes of 2-20nm in the described carbon nanotube conducting agent powder.
3. method for preparing lithium ion battery pole pieces according to claim 1 and 2 is characterized in that: in the carbon nano-tube slurry of described preparation, the weight content of carbon nano-tube is 2%-13.8%.
4. method for preparing lithium ion battery pole pieces according to claim 3, it is characterized in that: described surfactant is the surfactant of stable in properties in lithium ion battery battery chemical work voltage range, is in dispersant, defoamer, wetting agent, the levelling agent one or more.
5. method for preparing lithium ion battery pole pieces according to claim 4 is characterized in that: described defoamer is polysiloxanes or its modifier; Described wetting agent is a polyethenoxy alkylphenols; Described levelling agent is the polysilanes solvent.
6. method for preparing lithium ion battery pole pieces according to claim 4, it is characterized in that: described carbon nano-tube slurry is divided into aqueous slurry and oil is slurry, during the preparation aqueous slurry, solvent is at least a in deionized water, the isopropyl alcohol, and described dispersant is a kind of in polyoxyethylene ether block copolymers, polyamine salt, the alcohols; Make up oil when being slurry, solvent is one or more in N-methyl pyrrolidone, cyclohexanone, acetone, the isopropyl alcohol, and described dispersant is one or more in polysiloxanes and modifier thereof, polyamine salt, organic solvent, the polypyrrole alkane ketone.
7. method for preparing lithium ion battery pole pieces according to claim 6 is characterized in that: described carbon nano-tube oil is that slurry is used to prepare anode pole piece or cathode pole piece; Described carbon nano-tube aqueous slurry is used to prepare cathode pole piece.
8. method for preparing lithium ion battery pole pieces according to claim 1, it is characterized in that: described carbon nano-tube has different additions to different active materials, solid part weight by the pole piece slurry for preparing, the addition of carbon nano-tube is: when negative active core-shell material was graphite, carbon nano-tube was 0.1-3.0%; When negative active core-shell material was lithium titanate, carbon nano-tube was 0.5-5.0%; When positive electrode active materials was cobalt acid lithium, carbon nano-tube was 0.2-5.0%; When positive electrode active materials was lithium nickelate, carbon nano-tube was 0.2-6.0%; When positive electrode active materials was lithium nickel cobalt multicomponent material, carbon nano-tube was 1.0-6.0%; When positive electrode active materials was LiFePO4, carbon nano-tube was 1.0-6.0%; When positive electrode active materials was lithium manganese phosphate, carbon nano-tube was 1.0-7.0%.
9. method for preparing lithium ion battery pole pieces according to claim 1 is characterized in that: in the described carbon nano-tube powder, metals content impurity is lower than 1% by dry state weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010591312.6A CN102195032B (en) | 2010-12-16 | 2010-12-16 | Method for preparing lithium ion battery pole pieces |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010591312.6A CN102195032B (en) | 2010-12-16 | 2010-12-16 | Method for preparing lithium ion battery pole pieces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102195032A true CN102195032A (en) | 2011-09-21 |
| CN102195032B CN102195032B (en) | 2016-05-04 |
Family
ID=44602720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010591312.6A Active CN102195032B (en) | 2010-12-16 | 2010-12-16 | Method for preparing lithium ion battery pole pieces |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102195032B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000956A (en) * | 2012-11-29 | 2013-03-27 | 东莞新能源科技有限公司 | Manufacturing method of lithium ion battery containing gel electrolyte |
| CN104282911A (en) * | 2014-07-31 | 2015-01-14 | 珠海银隆新能源有限公司 | Preparation method of positive sizing agent of lithium ion battery, positive electrode sheet and lithium ion battery |
| CN105826512A (en) * | 2015-01-08 | 2016-08-03 | 中信国安盟固利动力科技有限公司 | Method for increasing cycle life of lithium ion battery based on thermal conductivity |
| CN106654282A (en) * | 2017-01-23 | 2017-05-10 | 合肥国轩高科动力能源有限公司 | Carbon nanotube anode slurry and slurry mixing method thereof |
| CN107799772A (en) * | 2016-08-30 | 2018-03-13 | 深圳市沃特玛电池有限公司 | A kind of low temperature resistant lithium ion battery |
| CN108428925A (en) * | 2018-02-11 | 2018-08-21 | 广西卓能新能源科技有限公司 | It is a kind of big than energy lithium battery and preparation method thereof |
| CN109638212A (en) * | 2018-11-20 | 2019-04-16 | 东莞锂威能源科技有限公司 | A kind of high magnification fast charge lithium ion battery |
| CN109713308A (en) * | 2018-12-19 | 2019-05-03 | 浙江中科立德新材料有限公司 | A kind of aqueous lithium cell size and preparation method thereof containing CNT |
| CN109920983A (en) * | 2017-12-12 | 2019-06-21 | 财团法人工业技术研究院 | The forming method of positive plate and positive plate slurry |
| CN110380016A (en) * | 2019-06-04 | 2019-10-25 | 深圳烯湾科技有限公司 | Carbon nanotube aqueous slurry, carbon nanotube silicon carbon material and preparation method thereof |
| WO2020211452A1 (en) * | 2019-04-15 | 2020-10-22 | 宁德时代新能源科技股份有限公司 | Positive pole piece, electrochemical device and device |
| CN112086622A (en) * | 2020-09-29 | 2020-12-15 | 珠海冠宇电池股份有限公司 | Lithium battery negative plate, preparation method thereof and lithium battery |
| CN113571256A (en) * | 2021-07-22 | 2021-10-29 | 哈尔滨万鑫石墨谷科技有限公司 | Aqueous carbon nanotube slurry and preparation method and application thereof |
| US11196041B2 (en) | 2018-09-28 | 2021-12-07 | Contemporary Amperex Technology Co., Limited | Positive electrode plate and lithium-ion secondary battery |
| CN114122403A (en) * | 2021-11-19 | 2022-03-01 | 江苏海基新能源股份有限公司 | Lithium ion battery anode slurry, anode plate and lithium ion battery |
| CN114284465A (en) * | 2021-12-22 | 2022-04-05 | 蜂巢能源科技股份有限公司 | Preparation method of positive electrode slurry, positive electrode plate and lithium ion battery |
| US12051811B2 (en) | 2018-12-29 | 2024-07-30 | Contemporary Amperex Technology Co., Limited | Electrode plate, electrochemical apparatus, battery module, battery pack, and device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005285731A (en) * | 2004-03-29 | 2005-10-13 | Masayuki Yoshio | Battery constituting material |
| CN1819307A (en) * | 2004-11-08 | 2006-08-16 | 爱来克株式会社 | Positive electrode for lithium cell and lithium cell using same |
| CN101132062A (en) * | 2006-08-24 | 2008-02-27 | 比亚迪股份有限公司 | Electrode slurry preparing method |
| US20100028773A1 (en) * | 2007-03-05 | 2010-02-04 | Toyo Ink Mfg. Co., Ltd. | Composition for battery |
| CN101771165A (en) * | 2010-02-08 | 2010-07-07 | 中南大学 | Cylindrical lithium-ion power battery and preparation method thereof |
-
2010
- 2010-12-16 CN CN201010591312.6A patent/CN102195032B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005285731A (en) * | 2004-03-29 | 2005-10-13 | Masayuki Yoshio | Battery constituting material |
| CN1819307A (en) * | 2004-11-08 | 2006-08-16 | 爱来克株式会社 | Positive electrode for lithium cell and lithium cell using same |
| CN101132062A (en) * | 2006-08-24 | 2008-02-27 | 比亚迪股份有限公司 | Electrode slurry preparing method |
| US20100028773A1 (en) * | 2007-03-05 | 2010-02-04 | Toyo Ink Mfg. Co., Ltd. | Composition for battery |
| CN101771165A (en) * | 2010-02-08 | 2010-07-07 | 中南大学 | Cylindrical lithium-ion power battery and preparation method thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000956B (en) * | 2012-11-29 | 2016-04-27 | 东莞新能源科技有限公司 | A kind of manufacture method of the lithium ion battery containing gel electrolyte |
| CN103000956A (en) * | 2012-11-29 | 2013-03-27 | 东莞新能源科技有限公司 | Manufacturing method of lithium ion battery containing gel electrolyte |
| CN104282911A (en) * | 2014-07-31 | 2015-01-14 | 珠海银隆新能源有限公司 | Preparation method of positive sizing agent of lithium ion battery, positive electrode sheet and lithium ion battery |
| CN105826512A (en) * | 2015-01-08 | 2016-08-03 | 中信国安盟固利动力科技有限公司 | Method for increasing cycle life of lithium ion battery based on thermal conductivity |
| CN107799772A (en) * | 2016-08-30 | 2018-03-13 | 深圳市沃特玛电池有限公司 | A kind of low temperature resistant lithium ion battery |
| CN106654282A (en) * | 2017-01-23 | 2017-05-10 | 合肥国轩高科动力能源有限公司 | Carbon nanotube anode slurry and slurry mixing method thereof |
| CN109920983A (en) * | 2017-12-12 | 2019-06-21 | 财团法人工业技术研究院 | The forming method of positive plate and positive plate slurry |
| CN109920983B (en) * | 2017-12-12 | 2021-08-06 | 财团法人工业技术研究院 | Positive plate and method for forming positive plate slurry |
| CN108428925A (en) * | 2018-02-11 | 2018-08-21 | 广西卓能新能源科技有限公司 | It is a kind of big than energy lithium battery and preparation method thereof |
| US11196041B2 (en) | 2018-09-28 | 2021-12-07 | Contemporary Amperex Technology Co., Limited | Positive electrode plate and lithium-ion secondary battery |
| CN109638212A (en) * | 2018-11-20 | 2019-04-16 | 东莞锂威能源科技有限公司 | A kind of high magnification fast charge lithium ion battery |
| CN109713308A (en) * | 2018-12-19 | 2019-05-03 | 浙江中科立德新材料有限公司 | A kind of aqueous lithium cell size and preparation method thereof containing CNT |
| CN109713308B (en) * | 2018-12-19 | 2022-04-05 | 浙江中科立德新材料有限公司 | CNT-containing aqueous lithium battery slurry and preparation method thereof |
| US12051811B2 (en) | 2018-12-29 | 2024-07-30 | Contemporary Amperex Technology Co., Limited | Electrode plate, electrochemical apparatus, battery module, battery pack, and device |
| WO2020211452A1 (en) * | 2019-04-15 | 2020-10-22 | 宁德时代新能源科技股份有限公司 | Positive pole piece, electrochemical device and device |
| CN110380016A (en) * | 2019-06-04 | 2019-10-25 | 深圳烯湾科技有限公司 | Carbon nanotube aqueous slurry, carbon nanotube silicon carbon material and preparation method thereof |
| CN112086622A (en) * | 2020-09-29 | 2020-12-15 | 珠海冠宇电池股份有限公司 | Lithium battery negative plate, preparation method thereof and lithium battery |
| CN113571256A (en) * | 2021-07-22 | 2021-10-29 | 哈尔滨万鑫石墨谷科技有限公司 | Aqueous carbon nanotube slurry and preparation method and application thereof |
| CN114122403A (en) * | 2021-11-19 | 2022-03-01 | 江苏海基新能源股份有限公司 | Lithium ion battery anode slurry, anode plate and lithium ion battery |
| CN114284465A (en) * | 2021-12-22 | 2022-04-05 | 蜂巢能源科技股份有限公司 | Preparation method of positive electrode slurry, positive electrode plate and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102195032B (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102195032B (en) | Method for preparing lithium ion battery pole pieces | |
| CN107799699B (en) | Clay mineral composite lithium battery diaphragm and preparation method thereof | |
| Qin et al. | Ni (OH) 2/CNTs hierarchical spheres for a foldable all-solid-state supercapacitor with high specific energy | |
| CN108448080B (en) | Graphene-coated silicon/metal composite negative electrode material and preparation method thereof | |
| US20140162121A1 (en) | Powder for cathode of lithium-sulfur secondary battery and method of fabricating the same | |
| CN105161676A (en) | Preparation method for lithium iron phosphate cathode slurry | |
| CN105355884B (en) | Height ratio capacity lithium ion battery electrode material and preparation method thereof | |
| CN105024044A (en) | Preparation method of high-capacity silica-powder-doped lithium battery anode slurry | |
| CN104716312A (en) | Silicon-carbon composite material for lithium ion battery, preparation method and application of silicon-carbon composite material | |
| CN105070915A (en) | Method for preparing lithium battery graphite cathode slurry | |
| CN103531814B (en) | Composite conductive agent and dispersion method thereof as well as positive plate and lithium ion battery | |
| CN105932284B (en) | A kind of close cladded type composite material and preparation method of mesoporous carbon and application | |
| CN105161675A (en) | Preparation method for lithium titanate negative electrode slurry of lithium battery | |
| Fan et al. | One‐pot hydrothermal synthesis of ZnS nanospheres anchored on 3D conductive MWCNTs networks as high‐rate and cold‐resistant anode materials for sodium‐ion batteries | |
| CN105161770A (en) | Lead plaster additive for lead-acid storage battery, and preparation method and application therefor | |
| Jin et al. | Pomegranate-like Li3VO4/3D graphene networks nanocomposite as lithium ion battery anode with long cycle life and high-rate capability | |
| CN105206790A (en) | Preparation method for lithium battery anode slurry doped with tin powder | |
| CN104835941A (en) | Preparation method of graphene-doped lead acid battery lead paste | |
| CN106654171A (en) | A composite dispersant, lithium ion battery anode slurry, an anode and a lithium ion battery | |
| Zeng et al. | Soft-templating and hydrothermal synthesis of NiCo 2 O 4 nanomaterials on Ni foam for high-performance supercapacitors | |
| Wu et al. | Zinc–carbon paper composites as anodes for Zn-ion batteries: key impacts on their electrochemical behaviors | |
| CN107248451A (en) | A kind of lithium-ion capacitor of high-energy-density | |
| CN105390683A (en) | Sulfur-based negative electrode material of lithium ion batteries and application thereof | |
| CN111129500A (en) | Preparation method of aqueous composite carbon nanotube conductive slurry | |
| CN110957494A (en) | Graphene lithium ion battery conductive agent 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180622 Address after: 352100 Xingang Road, Zhangwan Town, Jiaocheng District, Ningde, Fujian 1 Patentee after: Ningde Amperex Technology Ltd. Address before: 523080 new energy technology park, Baima management area, Nancheng District, Dongguan, Guangdong Patentee before: Dongguan New Energy Source Electronic Sci-Tech Co., Ltd. |