CN103022417A - Anode material of lithium-ion cell - Google Patents
Anode material of lithium-ion cell Download PDFInfo
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Abstract
The invention relates to the technical field of lithium-ion cells, and in particular relates to a positive pole material of a lithium-ion cell and a preparation method of the positive pole material. The positive pole material comprises the following components in percentage by weight: 96.5-98.6% of lithium cobalt oxide, 0.8-2.0% of a binding agent and 0.6-1.5% of a carbon fiber tube. According to the preparation method, the carbon nano tube is used as a conductive agent, the use addition amount of the conductive agent is reduced, the preparation is simple, the performance of a prepared product is stable, particularly the specific capacity is high, and the positive pole material is suitable for requirements of high specific capacity of the battery in modern portable electrical equipment.
Description
Technical field
The present invention relates to the lithium-ion electric core technical field, relate in particular to a kind of lithium-ion electric core positive electrode and preparation method thereof.
Background technology
Lithium-ion electric core has become the focus and emphasis of international battery core circle commodity development because its high-energy-density and high-tension advantage have received people's very big concern.At present, lithium-ion electric core has been widely used in the fields such as mobile communication, portable notebook computer, video camera, portable instrument, and is along with energetic, the lightweight of these electrical equipment, also more and more urgent to the high power capacity demand of lithium-ion electric core.Cobalt acid lithium has the following advantages, structure is good, being fit to lithium ion embeds, and mature preparation process, open circuit voltage is high, the energy fast charging and discharging, chemical property is superior: specific energy is high, have extended cycle life, processing characteristics is excellent, product structure and stable performance, high conformity, with low cost, without any poisonous and harmful substance, can to characteristics such as any pollutions of environment structure, be not the widely used good lithium-ion electric core positive electrodes such as portable electronics such as notebook computer, mobile phone, video camera.
Carbon nano-tube has another name called Baji-tube, is a kind of One-dimensional Quantum material with special construction, has typical stratiform hollow structure feature, and there is the end cap sealing at the two ends of general pipe.Carbon nano-tube has good electric conductivity, because the structure of carbon nano-tube is identical with the lamellar structure of graphite, so have good electric property.The direction of atomic arrangement vector (n, m) expression commonly used on the carbon nano-tube, the p electronics of carbon atom forms large-scale delocalized bond on the carbon nano-tube, because conjugation is remarkable, for the n=m direction, carbon nano-tube shows good conductivity, and conductivity can reach 10,000 times of copper usually.Carbon nano-tube is applied in the lithium-ion electric core, because its conductivity is higher than the carbon black conductive agent far away, so its composition in prescription needs only a seldom part.
Present anode material for lithium-ion batteries adopts cobalt acid lithium and carbon black conductive agent to arrange in pairs or groups mostly, and wherein the shared proportion of carbon black is larger.Patent CN101083340A lithium-ion-power cell, in parts by weight, its anodal proportioning is: cobalt acid lithium 720-800, LiMn2O4 175-240, conductive agent 12-35, solvent 420-650, described conductive agent are any one or the combinations in electrically conductive graphite, the conductive black, and it has rational in infrastructure, lightweight, security performance is good, and capacity is high, and internal resistance is little, but heavy-current discharge is for equipment provides the higher characteristics such as power.But wherein the conductive agent proportion is higher, and with respect to carbon fiber pipe, the conductivity of electrically conductive graphite and conductive black is relatively poor, so its proportion in proportioning is higher, has affected the proportion of cobalt acid lithium in proportioning, and battery capacity is reduced.
Summary of the invention
Technical problem to be solved by this invention is, overcome the defective that above-mentioned prior art exists, in anode material for lithium-ion batteries, by cobalt acid lithium and carbon nano-tube collocation are used, can improve the mixed powder gram volume of positive electrode, further increase the specific capacity of lithium-ion electric core.Produce a kind of high capacity polymer lithium-ion electric core by the method, can better be applied to portable electronics such as notebook computer, mobile phone, video camera etc.
To achieve these goals, technical scheme of the present invention is as follows: a kind of lithium-ion electric core positive electrode by weight percentage, comprises cobalt acid lithium 96.5%-98.6%, binding agent 0.8%-2.0% and carbon fiber pipe 0.6%-1.5%.
Preferably, described binding agent is Kynoar, and the solvent that described positive electrode adopts is 1-METHYLPYRROLIDONE.
The preparation method of described lithium-ion electric core positive electrode may further comprise the steps:
A, the binding agent of formula ratio and 10-20 times of weight solvent of weight of binder are added in a mixing bowl, with revolution: 30-40 revolutions per second; After rotation: 25-30 revolutions per second speed is stirred to binding agent and fully is dissolved in the solvent, add the carbon nano-tube of described formula ratio, with revolution: 30-40 revolutions per second; Rotation: 25-30 revolutions per second speed stirred 4-5 hour, until in the conductive agent Uniform Dispersion solution;
B, the cobalt of formula ratio acid lithium is joined in a mixing bowl, with revolution: 30-40 revolutions per second; Rotation: 25-30 revolutions per second speed stirred 3-5 hour, and being uniformly dispersed to cobalt acid lithium makes suspension;
C, add solvent until be stirred to 0.5-1h after the described concentration in the suspension, namely obtain lithium ion battery anode glue size.
Preferably, described binding agent is Kynoar (being called for short PVDF), and described solvent is 1-METHYLPYRROLIDONE, and the solid content of described lithium-ion electric core anode sizing agent is 68-76%.
Preferably, before described steps A, also comprise step: described carbon nano-tube was processed 2-10 hour through frosted.
Preferably, among the described step B, divide 3-5 to criticize cobalt acid lithium and join in a mixing bowl, added once every 1 hour.
Preferably, behind described step C, also comprise step: described anode sizing agent is crossed 150 mesh sieves 2-3 time.
Beneficial effect of the present invention: utilize cobalt acid lithium to do the positive electrode of battery core, its have have extended cycle life, Stability Analysis of Structures, security performance are good, can not pollute environment structure; Use carbon fiber pipe to be conductive agent, reduced the addition of conductive agent under the equal in quality, the addition of cobalt acid lithium in the positive electrode is increased, improved the gram volume of the mixed powder of positive electrode, further improved the capacitance of lithium-ion electric core.
Description of drawings
Fig. 1 is 930mAh multiplying power resolution chart of the present invention;
Fig. 2 is 1000mAh multiplying power resolution chart of the present invention;
Fig. 3 is 930mAh loop test figure of the present invention;
Fig. 4 is 1000mAh loop test figure of the present invention.
Embodiment
Below in conjunction with specific embodiment the specific embodiment of the present invention is described in further detail.
Embodiment 1
A kind of lithium-ion electric core positive electrode comprises cobalt acid lithium 96.5%, carbon fiber pipe 1.5% and PVDF2.0% that percentage by weight calculates.
Described lithium-ion electric core positive electrode preparation process is as follows:
A, the binding agent of formula ratio and 10 times of weight 1-METHYLPYRROLIDONEs (NMP) of weight of binder are added in a mixing bowl, to revolve round the sun 30 revolutions per seconds; After the speed that rotation is 25 revolutions per seconds is stirred to binding agent and fully is dissolved in the solvent, add the carbon nano-tube of formula ratio, to revolve round the sun 30 revolutions per seconds; The speed that rotation is 25 revolutions per seconds stirred 5 hours, until in the conductive agent Uniform Dispersion solution;
B, the cobalt of formula ratio acid lithium is joined in a mixing bowl, to revolve round the sun 30 revolutions per seconds; The speed that rotation is 25 revolutions per seconds stirred 3 hours, and being uniformly dispersed to cobalt acid lithium makes suspension;
C, add solvent until be stirred to 0.5h after the described concentration in the suspension, namely obtain lithium ion battery anode glue size.
Wherein the solid content of gained lithium-ion electric core positive electrode is 68%.
The coating of lithium ion anode pole piece: according to the requirement of battery core pole piece surface density, the positive electrode slurry evenly is coated on plus plate current-collecting body, coating method adopts the coating of roll-in clearance-type, reserve the lug position according to the pole piece designing requirement, anode sizing agent coating used thickness is the aluminium foil of 16-30 μ m, anodal coated face density is 10g/m2, and anodal coating baking temperature is 90-120 ℃; To determine coated face density by the examination coating during coating, note during coating that cut can not be arranged, leak the foil phenomenon, will control simultaneously horizontal and vertical coating homogeneity.The baking of positive plate: pole piece toasts under positive dummy status, baking temperature 110-130 ℃, toasted 12 hours, in bake process every 4 hours continuous extraction argon gas 3 times, remove on the one hand in the baking box solvent and the moisture that toast out in the pole piece, can keep the baking box inner drying on the other hand, make the pole piece baking more abundant.Baking is carried out the extraction argon gas 3 times after finishing again continuously, then below the cooling pole piece to 40, takes out pole piece and carries out following process under vacuum state.
Embodiment 2
A kind of lithium-ion electric core positive electrode comprises 1-METHYLPYRROLIDONE (NMP) the solvent configuration anode sizing agent that percentage by weight calculates, and the material components by weight percentage of employing is: cobalt acid lithium 98.6%, carbon fiber pipe 0.6% and PVDF0.8%.
Described lithium-ion electric core positive electrode preparation process is as follows:
First carbon nano-tube was processed 4 hours through frosted;
A, the binding agent of formula ratio and 20 times of weight 1-METHYLPYRROLIDONEs (NMP) of weight of binder are added in a mixing bowl, to revolve round the sun 40 revolutions per seconds; After the speed that rotation is 30 revolutions per seconds is stirred to binding agent and fully is dissolved in the solvent, add the carbon nano-tube of formula ratio, to revolve round the sun 40 revolutions per seconds; The speed that rotation is 26 revolutions per seconds stirred 5 hours, until in the conductive agent Uniform Dispersion solution;
B, the cobalt of formula ratio acid lithium is joined in a mixing bowl, to revolve round the sun 40 revolutions per seconds; The speed that rotation is 30 revolutions per seconds stirred 3 hours, and being uniformly dispersed to cobalt acid lithium makes suspension;
C, add solvent until be stirred to 0.5h after the described concentration in the suspension, namely obtain lithium ion battery anode glue size.
Wherein the solid content of gained lithium-ion electric core positive electrode is 76%.
The coating process of lithium-ion electric core positive plate is identical with embodiment 1.
A kind of lithium-ion electric core positive electrode comprises 1-METHYLPYRROLIDONE (NMP) the solvent configuration anode sizing agent that percentage by weight calculates, and the material components by weight percentage of employing is: cobalt acid lithium 97.5%, carbon fiber pipe 1.5% and PVDF1.0%.
Described lithium-ion electric core positive electrode preparation process is as follows:
First carbon nano-tube was processed 2 hours through frosted;
A, the binding agent of formula ratio and 12 times of weight 1-METHYLPYRROLIDONEs (NMP) of weight of binder are added in a mixing bowl, to revolve round the sun 35 revolutions per seconds; After the speed that rotation is 28 revolutions per seconds is stirred to binding agent and fully is dissolved in the solvent, add the carbon nano-tube of formula ratio, to revolve round the sun 34 revolutions per seconds; The speed that rotation is 27 revolutions per seconds stirred 5 hours, until in the conductive agent Uniform Dispersion solution;
B, the cobalt of formula ratio acid lithium is joined in a mixing bowl, to revolve round the sun 35 revolutions per seconds; The speed that rotation is 27 revolutions per seconds stirred 3 hours, and being uniformly dispersed to cobalt acid lithium makes suspension;
C, add solvent until be stirred to 0.5h after the described concentration in the suspension, namely obtain lithium ion battery anode glue size.
Wherein the solid content of gained lithium-ion electric core positive electrode is 70%.
The coating process of lithium-ion electric core positive plate is identical with embodiment 1.
Embodiment 4
A kind of lithium-ion electric core positive electrode comprises 1-METHYLPYRROLIDONE (NMP) the solvent configuration anode sizing agent that percentage by weight calculates, and the material components by weight percentage of employing is: cobalt acid lithium 97.6%, carbon fiber pipe 1.2% and PVDF1.2%.
Described lithium-ion electric core positive electrode preparation process is as follows:
First carbon nano-tube was processed 10 hours through frosted;
A, the binding agent of formula ratio and 14 times of weight 1-METHYLPYRROLIDONEs (NMP) of weight of binder are added in a mixing bowl, to revolve round the sun 32 revolutions per seconds; After the speed that rotation is 26 revolutions per seconds is stirred to binding agent and fully is dissolved in the solvent, add the carbon nano-tube of formula ratio, to revolve round the sun 38 revolutions per seconds; The speed that rotation is 28 revolutions per seconds stirred 5 hours, until in the conductive agent Uniform Dispersion solution;
B, the cobalt of formula ratio acid lithium is joined in a mixing bowl, to revolve round the sun 36 revolutions per seconds; The speed that rotation is 29 revolutions per seconds stirred 3 hours, and being uniformly dispersed to cobalt acid lithium makes suspension;
C, add solvent until be stirred to 0.5h after the described concentration in the suspension, namely obtain lithium ion battery anode glue size.
Wherein the solid content of gained lithium-ion electric core positive electrode is 45%.
The coating process of lithium-ion electric core positive plate is identical with embodiment 1.
Embodiment 5
A kind of lithium-ion electric core positive electrode comprises 1-METHYLPYRROLIDONE (NMP) the solvent configuration anode sizing agent that percentage by weight calculates, and the material components by weight percentage of employing is: cobalt acid lithium 97.2%, carbon fiber pipe 1.4% and PVDF1.4%.
Described lithium-ion electric core positive electrode preparation process is as follows:
First carbon nano-tube was processed 5 hours through frosted;
A, the binding agent of formula ratio and 18 times of weight 1-METHYLPYRROLIDONEs (NMP) of weight of binder are added in a mixing bowl, to revolve round the sun 36 revolutions per seconds; After the speed that rotation is 27 revolutions per seconds is stirred to binding agent and fully is dissolved in the solvent, add the carbon nano-tube of formula ratio, to revolve round the sun 35 revolutions per seconds; The speed that rotation is 30 revolutions per seconds stirred 5 hours, until in the conductive agent Uniform Dispersion solution;
B, the cobalt of formula ratio acid lithium is joined in a mixing bowl, to revolve round the sun 38 revolutions per seconds; The speed that rotation is 26 revolutions per seconds stirred 3 hours, and being uniformly dispersed to cobalt acid lithium makes suspension;
C, add solvent until be stirred to 0.5h after the described concentration in the suspension, namely obtain lithium ion battery anode glue size.
Wherein the solid content of gained lithium-ion electric core positive electrode is 42%.
The coating process of lithium-ion electric core positive plate is identical with embodiment 1.
Above-described embodiment is preferred embodiment of the present invention, is not to limit the scope of the present invention, so all equivalences of being done with the described structure of claim of the present invention, feature and principle change or modify, all should be included within the claim scope of the present invention.
Comparative Examples
A kind of preparation method of lithium-ion electric core positive electrode: 1-METHYLPYRROLIDONE (NMP) solvent configuration anode sizing agent, the material components by weight percentage of employing is: cobalt acid lithium 86-90%, binding agent 2.5-3.5%, conductive carbon black (S-P) 1.5-5% and electrically conductive graphite 0.5-10%.
Adopting the every gram capacitance of mixture of the lithium-ion electric core of making in the Comparative Examples is 134.2-135.9mAh/g, and the every gram capacitance of mixture of the positive electrode of the lithium-ion electric core positive pole of the formula Design of employing embodiment of the invention 1-5 is 137.0-140.0mAh/g, and every gram capacitance of the average positive electrode mixture of battery core formula Design of the present invention is than the high 2.1-5.8mAh/g of Comparative Examples.
Select the 523450AR model to set same battery core volume, adopt at present existing formula Design can only do the 930mAh capacity, adopt the present invention's CNTs design of newly filling a prescription, can do the 1000mAh capacity, its multiplying power loop-around data and curve are as follows:
523450AR model 930mAh capacity, adopt at present existing formula Design battery core multiplying power data:
| Model | Nominal capacity (mAh) | Discharge-rate (C) | Discharge capacity (mAh) | Volume percent (%) |
| 523450AR | 930 | 0.2C | 1006 | 100.0% |
| 523450AR | 930 | 0.5C | 984 | 97.8% |
| 523450AR | 930 | 1C | 959 | 95.3% |
| 523450AR | 930 | 2C | 902 | 89.7% |
523450AR model 1000mAh capacity, adopt the present invention's CNTs design battery core multiplying power data of newly filling a prescription:
| Model | Nominal capacity (mAh) | Discharge-rate (C) | Discharge capacity (mAh) | Volume percent (%) |
| |
1000 | 0.2C | 1006 | 100.0 |
| 523450AR | ||||
| 1000 | 0.5C | 1002 | 99.6 | |
| 523450AR | ||||
| 1000 | 1C | 1002 | 99.6 | |
| 523450AR | ||||
| 1000 | 2C | 967 | 96.1% |
As can be seen from the above data: the 523450AR model is set same battery core volume, adopts the present invention's CNTs design battery core multiplying power of newly filling a prescription to be better than and to adopt at present existing formula Design battery core multiplying power.
523450AR model 930mAh capacity, adopt at present existing formula Design battery core 1C cycle performance data:
| Model | Nominal capacity (mAh) | Test condition | Cycle-index | Initial capacity (mAh) | Capacity (mAh) after surveying | Volume percent (%) |
| 523450AR | 930 | 1C charges and discharge | 300 | 955 | 771 | 80.7% |
523450AR model 1000mAh capacity, adopt the present invention's CNTs design battery core 1C cycle performance data of newly filling a prescription:
| Model | Nominal capacity (mAh) | Test condition | Cycle-index | Initial capacity (mAh) | Capacity (mAh) after surveying | Volume percent (%) |
| |
1000 | 1C charges and discharge | 300 | 1050 | 920 | 87.6% |
As can be seen from the above data: the 523450AR model is set same battery core volume, adopts the present invention's CNTs design battery core 1C cycle performance of newly filling a prescription to be better than and to adopt at present existing formula Design battery core 1C cycle performance.
Claims (8)
1. a lithium-ion electric core positive electrode is characterized in that: count by weight percentage, comprise cobalt acid lithium 96.5%-98.6%, binding agent 0.8%-2.0% and carbon fiber pipe 0.6%-1.5%.
2. lithium-ion electric core positive electrode according to claim 1, it is characterized in that: described binding agent is Kynoar.
3. lithium-ion electric core positive electrode according to claim 1 is characterized in that: described 1-METHYLPYRROLIDONE solvent.
4. the preparation method of the described lithium-ion electric core positive electrode of any one according to claim 1-3 may further comprise the steps:
A, the binding agent of formula ratio and 10-20 times of weight solvent of weight of binder are added in a mixing bowl, with 30-40 revolutions per second of revolution; After rotation 25-30 revolutions per second speed is stirred to binding agent and fully is dissolved in the solvent, add the carbon nano-tube of described formula ratio, with 30-40 revolutions per second of revolution; Rotation 25-30 revolutions per second speed stirred 4-5 hour, until in the conductive agent Uniform Dispersion solution;
B, the cobalt of formula ratio acid lithium is joined in a mixing bowl, with 30-40 revolutions per second of revolution; Rotation 25-30 revolutions per second speed stirred 3-5 hour, and being uniformly dispersed to cobalt acid lithium makes suspension;
C, be stirred to 0.5-1h after adding residual solvent in the suspension, namely obtain described anode material for lithium-ion batteries.
5. the preparation method of lithium-ion electric core positive electrode according to claim 4 is characterized in that: also comprised step before described steps A: described carbon nano-tube was processed 2-10 hour through frosted.
6. the preparation method of lithium-ion electric core positive electrode according to claim 4, it is characterized in that: the solid content of described lithium-ion electric core anode sizing agent is 68-76%.
7. the preparation method of lithium-ion electric core positive electrode according to claim 4 is characterized in that: behind described step C, also comprise step: described anode sizing agent is crossed 150 mesh sieves 2-3 time.
8. a right to use requires the battery core of 1 described lithium-ion electric core positive electrode.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779602A (en) * | 2014-02-13 | 2014-05-07 | 东莞市安德丰电池有限公司 | Lithium ion battery and preparation method thereof |
| CN104362346A (en) * | 2014-10-14 | 2015-02-18 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN104600241A (en) * | 2014-12-17 | 2015-05-06 | 深圳市比克电池有限公司 | Lithium ion battery positive plate, preparation method of lithium ion battery positive plate, and lithium ion battery |
| CN109411114A (en) * | 2018-09-19 | 2019-03-01 | 惠州市轻益科技有限公司 | A kind of super conductive paste and preparation method thereof suitable for lithium ion battery production |
| CN109524616A (en) * | 2018-10-31 | 2019-03-26 | 中航锂电（洛阳）有限公司 | A kind of lithium ion battery anode glue size and preparation method thereof |
| CN115458797A (en) * | 2022-10-27 | 2022-12-09 | 欣旺达电动汽车电池有限公司 | Secondary battery and electric equipment |
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| CN1819308A (en) * | 2006-03-15 | 2006-08-16 | 上海南都能源科技有限公司 | Lithium ion battery pole piece with high multiplying power and production thereof |
| CN101071859A (en) * | 2007-06-07 | 2007-11-14 | 深圳市邦凯电子有限公司 | Lithium cell anode active substance, anode dressing and its preparing method |
| CN101425576A (en) * | 2008-12-02 | 2009-05-06 | 黄德欢 | Preparing method of highly conductive lithium iron anode material of lithium ionic cell |
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| CN1819308A (en) * | 2006-03-15 | 2006-08-16 | 上海南都能源科技有限公司 | Lithium ion battery pole piece with high multiplying power and production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103779602A (en) * | 2014-02-13 | 2014-05-07 | 东莞市安德丰电池有限公司 | Lithium ion battery and preparation method thereof |
| CN104362346A (en) * | 2014-10-14 | 2015-02-18 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN104600241A (en) * | 2014-12-17 | 2015-05-06 | 深圳市比克电池有限公司 | Lithium ion battery positive plate, preparation method of lithium ion battery positive plate, and lithium ion battery |
| CN109411114A (en) * | 2018-09-19 | 2019-03-01 | 惠州市轻益科技有限公司 | A kind of super conductive paste and preparation method thereof suitable for lithium ion battery production |
| CN109524616A (en) * | 2018-10-31 | 2019-03-26 | 中航锂电（洛阳）有限公司 | A kind of lithium ion battery anode glue size and preparation method thereof |
| CN115458797A (en) * | 2022-10-27 | 2022-12-09 | 欣旺达电动汽车电池有限公司 | Secondary battery and electric equipment |
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Application publication date: 20130403 |