CN104157827A - Lithium ion battery negative film and preparation method thereof - Google Patents
Lithium ion battery negative film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery negative film and a preparation method thereof. The preparation method comprises the following steps: dissolving a thickening agent in a solvent, adding a pore forming agent, and uniformly mixing to obtain a thickening agent mother liquid; adding a conductive agent, a negative active material and an adhesive into the thickening agent mother liquid, and uniformly stirring to obtain active slurry; coating the active slurry onto a current collector, and drying to form an active slurry layer which covers the current collector, thereby obtaining the lithium ion battery negative film. In the drying process of the pore forming agent, when the gas generated when the pore forming agent is volatilized escapes, pores can be formed in the surface of the lithium ion battery negative film; after the negative film is tightly compressed, the space for containing electrolyte is increased because of the pores in the surface of the negative film, the electrolyte can be easily infiltrated into the negative film, and thus the liquid injection efficiency of a lithium ion battery is improved. The invention further discloses the lithium ion battery negative film which is obtained by using the preparation method.
Description
Technical field
The present invention relates to lithium ion battery field, particularly relate to a kind of anode plate for lithium ionic cell and preparation method thereof.
Background technology
Lithium ion battery is taking carbon materials for as negative pole, taking the compound containing lithium as anodal.In the time that battery is charged, on the positive pole of battery, there is lithium ion to generate, the lithium ion of generation arrives negative pole through electrolyte movement; And be layer structure as the carbon of negative pole, and it has a lot of micropores, and the lithium ion that arrives negative pole is just embedded in the micropore of carbon-coating, and the lithium ion of embedding is more, and charging capacity is higher.Equally, in the time that battery is discharged, the lithium ion being embedded in negative pole carbon-coating is deviate from, and moves back again anodal, returns anodal lithium ion more, and discharge capacity is higher.
Along with the appearance of smart mobile phone and panel computer, people are more and more higher to the capacity requirement of lithium ion battery, require the service time of battery more and more longer.But under limited battery container volume, the capacity of battery is higher, the circulation of battery will be poorer.
Usually, the method for exploitation high-capacity battery is the compacting that improves anode plate for lithium ionic cell, but after negative plate compacting, just seldom, electrolyte is just difficult to infiltrate go to pole piece inside, has a strong impact on the fluid injection efficiency of lithium ion battery in the space on negative plate surface.
Summary of the invention
Based on this, be necessary to provide anode plate for lithium ionic cell that fluid injection efficiency is high after a kind of negative plate compacting and preparation method thereof.
A kind of anode plate for lithium ionic cell, comprises collector, and coats the active slurry layer of described collector, is formed with the hole that pore creating material forms in the time overflowing on described active slurry layer;
Described active slurry layer comprises the negative active core-shell material of routine by mass percentage 88-98%, thickener, the binding agent of 1.0-5% and the conductive agent of 0.5-2% of 0.5-5%.
Therein in an embodiment, described negative active core-shell material is selected from least one in carbon negative pole material, silicon based anode material and tin base cathode material, described thickener is sodium carboxymethylcellulose, described binding agent is polyvinyl alcohol or butadiene-styrene rubber, and described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube, Graphene, acetylene black, carbonaceous mesophase spherules and Ketjen black.
In an embodiment, described negative active core-shell material is selected from least one in native graphite, Delanium and carbonaceous mesophase spherules therein, and described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube and Graphene.
The preparation method of above-mentioned lithium ion negative plate, comprises the following steps:
Thickener is dissolved in solvent, adds pore creating material, mix, obtain thickener mother liquor, wherein, in described thickener mother liquor, the mass percent of described thickener is 0.5-10%, and the mass percent of described pore creating material is 1-10%;
In described thickener mother liquor, add conductive agent, negative active core-shell material and binding agent, stir, obtain active slurry;
Described active slurry is coated to collector, after dry, form the active slurry layer covering on described collector, obtain anode plate for lithium ionic cell, wherein, in described active slurry layer, the mass percent of described negative active core-shell material is 88-98%, and the mass fraction of described thickener is 0.5-5%, the mass percent of described binding agent is 1.0-5%, and the mass percent of described conductive agent is 0.5-2.0%.
In an embodiment, after described being dried, obtain being operating as of anode plate for lithium ionic cell therein: at 90-120 DEG C, the collector that is coated with described active slurry is dried, obtain described anode plate for lithium ionic cell.
In an embodiment, described pore creating material is selected from least one in n-butanol, isopropyl alcohol, ethanol and acetone therein.
In an embodiment, in described thickener mother liquor, the mass percent of described thickener is 1-2% therein, and the mass percent of described pore creating material is 1-5%.
Therein in an embodiment, in described active slurry layer, the mass percent of described negative active core-shell material is 95.5-97%, and the mass fraction of described thickener is 1.2-2.5%, the mass percent of described binding agent is 1-2.8%, and the mass percent of described conductive agent is 0.5-2.0%.
Therein in an embodiment, described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube, Graphene, acetylene black, carbonaceous mesophase spherules and Ketjen black, and described negative active core-shell material is selected from least one in carbon negative pole material, silicon based anode material and tin base cathode material.
In an embodiment, described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube and Graphene therein, and described negative active core-shell material is selected from least one in native graphite, Delanium and carbonaceous mesophase spherules.
Above-mentioned anode plate for lithium ionic cell adds pore creating material in preparation process, and described pore creating material is in dry run, and the gas producing due to its volatilization forms hole on lithium ion negative plate surface in the time overflowing.After negative plate is compacted, because existing hole, negative plate surface increases the space that can hold electrolyte, and electrolyte is easily infiltrated in pole piece, thereby improved the fluid injection efficiency of lithium ion battery.
In addition, adopt the lithium ion battery of above-mentioned negative plate, owing to resting on electrolyte in hole from negative plate diffusion into the surface to negative plate inside, reduced the polarization that brings because of concentration difference, improved circulation, multiplying power and the cryogenic property of lithium ion battery.
Brief description of the drawings
Fig. 1 is preparation method's flow chart of an execution mode anode plate for lithium ionic cell;
Fig. 2 is the polymer Li-ion battery of embodiment 1 and the circulation comparison diagram of control group polymer Li-ion battery.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
The anode plate for lithium ionic cell of one execution mode, comprise collector, and coat the active slurry layer of collector, and on active slurry layer, be formed with the hole that pore creating material forms in the time overflowing, wherein active slurry layer comprises negative active core-shell material, thickener, binding agent and conductive agent.
Negative active core-shell material is selected from least one in carbon negative pole material, silicon based anode material and tin base cathode material, wherein, carbon negative pole material comprises native graphite, Delanium and carbonaceous mesophase spherules etc., silicon based anode material comprises nano-silicon, thin film silicon and silicon based composite material etc., and tin base cathode material comprises oxide and the tinbase composite oxides of tin.Because carbon negative pole material specific capacity is high, have extended cycle life, carbon reserves are abundant, and cheap, in another embodiment, negative active core-shell material is selected from least one in native graphite, Delanium and carbonaceous mesophase spherules.The quality percentage composition of negative active core-shell material in active slurry layer is 90-98%.
Thickener be for increasing with the viscosity of improving thickener mother liquor.In one embodiment, thickener is sodium carboxymethylcellulose (Carboxyl methyl Cellulose, CMC), and CMC is all soluble and form viscous solution in cold water or hot water, and in long-time, viscosity can not change.The mass percent of thickener in active slurry layer is 0.5-10%.
Binding agent is the uniformity when ensureing negative active core-shell material slurrying, is conducive to keep the bonding stability between negative active core-shell material and collector.In one embodiment, binding agent is polyvinyl alcohol.Wherein, polyvinyl alcohol and CMC have good compatibility, can improve the uniformity of slurry.The mass percent of binding agent in active slurry is 1.5-5%.In another embodiment, binding agent is butadiene-styrene rubber.
Conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube, Graphene, acetylene black, carbonaceous mesophase spherules and Ketjen black.Conductive agent is in order to ensure that electrode has good charge-discharge performance, improves the mobility of lithium ion in electrode material, thereby improves the efficiency for charge-discharge of electrode.In another embodiment, conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube and Graphene.The mass percent of conductive agent in active slurry layer is 0.5-1.5%.
Above-mentioned anode plate for lithium ionic cell is because the active slurry layer of coating collector exists hole, make in the time that negative plate is compacted, the hole of active slurry layer can increase the spatial accommodation of electrolyte between negative plate and negative plate, electrolyte is easily infiltrated in pole piece, thereby improved the fluid injection efficiency of lithium ion battery.
In addition, adopt the lithium ion battery of above-mentioned negative plate, owing to resting on electrolyte in hole from negative plate diffusion into the surface to negative plate inside, reduced the polarization that brings because of concentration difference, improved circulation, multiplying power and the cryogenic property of lithium ion battery.
Above-mentioned lithium ion negative plate can be applicable to polymer Li-ion battery, aluminum steel housing battery and liquid soft-package battery.
As shown in Figure 1, the preparation method of the lithium ion negative plate of an execution mode, comprises the following steps:
Step S110, is dissolved in thickener in solvent, adds pore creating material, mixes, and obtains thickener mother liquor.
Pore creating material is to rely on its volatilization and in final products, form a class material of hole in when heating, in one embodiment, pore creating material is selected from least one in n-butanol, isopropyl alcohol, ethanol and acetone, being that pore creating material can be both the one in above-mentioned organic substance, can be also above-mentioned organic mixture.In another embodiment, pore creating material is n-butanol, the boiling point of n-butanol is 117.7 DEG C, and can form azeotropic mixture with water, azeotropic point is 92 DEG C, when active slurry is during at heating, drying, the n-butanol that forms azeotropic mixture with water can first volatilize, the effusion of volatilizing in the time reaching boiling point of the n-butanol of remaining part has avoided a large amount of n-butanols to volatilize simultaneously, has improved the uniformity of negative plate surface pore.
Thickener is sodium carboxymethylcellulose (Carboxyl methyl Cellulose, CMC), and CMC is all soluble and form viscous solution in cold water or hot water, and in long-time, viscosity can not change.
Solvent is the compound that water or other can dissolve thickener.
The size of thickener mother liquor solid content can affect the uniformity of follow-up slurry, and then affects the performance of negative plate.Solid content is the mass fraction that after emulsion is dried under rated condition, remainder accounts for total amount.The solid content of thickener mother liquor is the mass fraction of removing the content of thickener after pore creating material and solvent and account for thickener mother liquor.The solid content of thickener mother liquor can be controlled by the addition ratio that regulates thickener, solvent and pore creating material.In one embodiment, the solid content of thickener mother liquor is 0.5-5wt%, and viscosity is 500-10000mPas, and in the time preparing thickener mother liquor, the consumption of thickener is the 0.5-10% of thickener mother liquor quality, and the consumption of pore creating material is the 1-10% of thickener mother liquor quality.In another embodiment, the solid content of thickener mother liquor is 0.8-3wt%, and viscosity is 1000-9500mPas; In the time preparing thickener mother liquor, the consumption of thickener is the 1-5% of thickener mother liquor quality, and the consumption of pore creating material is the 0.5-5% of thickener mother liquor quality.In other embodiments, the solid content of thickener mother liquor is 1-2wt%, and viscosity is 1500-8500mPas; In the time preparing thickener mother liquor, the consumption of thickener is the 1-2% of thickener mother liquor quality, and the consumption of pore creating material is the 1-5% of thickener mother liquor quality.
Step S120 adds conductive agent, negative active core-shell material and binding agent in thickener mother liquor, stirs, and obtains active slurry.
Conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube, Graphene, acetylene black, carbonaceous mesophase spherules and Ketjen black.Conductive agent is in order to ensure that electrode has good charge-discharge performance, improves the mobility of lithium ion in electrode material, thereby improves the efficiency for charge-discharge of electrode.In another embodiment, conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube and Graphene.
Negative active core-shell material is selected from least one in carbon negative pole material, silicon based anode material and tin base cathode material, wherein, carbon negative pole material comprises native graphite, Delanium and carbonaceous mesophase spherules etc., silicon based anode material comprises nano-silicon, thin film silicon and silicon based composite material etc., and tin base cathode material comprises oxide and the tinbase composite oxides of tin.Because carbon negative pole material specific capacity is high, have extended cycle life, carbon reserves are abundant, and cheap, in one embodiment, negative active core-shell material is selected from least one in native graphite, Delanium and carbonaceous mesophase spherules.
Binding agent is the uniformity when ensureing negative active core-shell material slurrying, is conducive to keep the bonding stability between negative active core-shell material and collector.In one embodiment, binding agent is polyvinyl alcohol or polytetrafluoroethylene.Wherein, polyvinyl alcohol and CMC have good compatibility, can improve the uniformity of slurry.
Step S130, coats collector by active slurry, and the dry rear active slurry layer covering on described collector that forms, obtains anode plate for lithium ionic cell.
Collector refers to the structure or the part that collect electric current, such as Copper Foil or aluminium foil.Active slurry is coated to collector, and active slurry disperses to launch on collector, then, by dry the collector that is coated with active slurry, removes pore creating material and solvent, obtains active slurry layer.In one embodiment, the dry operation that obtains anode plate for lithium ionic cell is at 90-120 DEG C, the collector that is coated with described active slurry to be dried, when heating, pore creating material is overflowed with the form of gas, form hole on lithium ion negative plate surface, obtain having the active slurry layer of hole, collector has formed anode plate for lithium ionic cell with the active slurry layer of coating collector.
The uniformity of active slurry and stability are the key factors that affects lithium ion battery consistency and stability, therefore in active slurry, will control solid content and the viscosity of active slurry well preparing.The solid content of active slurry and viscosity can be by regulating the adding proportion between thickener mother liquor, conductive agent, negative active core-shell material and binding agent to control, in one embodiment, the solid content of active slurry is 35-60wt%, viscosity is 3000-8000mPas, in the active slurry layer obtaining, the mass percent of thickener, conductive agent, negative active core-shell material and binding agent is respectively 0.5-5%:0.5-2%:88-98%:0.5-5%.In another embodiment, the solid content of active slurry is 40-55wt%, viscosity is 4000-7000mPas, and in the active slurry layer obtaining, the mass percent of thickener, conductive agent, negative active core-shell material and binding agent is respectively 1-4%:0.5-2%:91-97%:1-3%.In other embodiments, the solid content of active slurry is 45-50wt%, viscosity is 4500-5000mPas, and in the active slurry layer obtaining, the mass percent of thickener, conductive agent, negative active core-shell material and binding agent is 1.2-2.5%:0.5-1.5%:95.5-97%:1-2.8%.
The preparation method of above-mentioned anode plate for lithium ionic cell adds pore creating material in preparation process, and described pore creating material is in dry run, and the gas producing due to its volatilization forms hole on lithium ion negative plate surface in the time overflowing.After negative plate is compacted, because negative plate surface exists hole, increase the space that can hold electrolyte, electrolyte is easily infiltrated in pole piece, thereby improved the fluid injection efficiency of lithium ion battery.
Further illustrate by specific embodiment below.
Embodiment 1
24.0g sodium carboxymethylcellulose (CMC) is joined in 2316g water, be stirred to dissolving, add 60g n-butanol, mix, obtain CMC mother liquor, wherein, the solid content of CMC mother liquor is that 1wt%, viscosity are 1000mPas.
Get the above-mentioned CMC mother liquor of 2400g, add 10g conductive carbon fibre, 1910g Delanium, 56g butadiene-styrene rubber, stirs, and obtains slurry, and wherein, the solid content of slurry is that 45.7wt%, viscosity are 4500mPas.
Get 2000g slurry and coat on Copper Foil, at 120 DEG C, dry, obtain anode plate for lithium ionic cell.
Above-mentioned anode plate for lithium ionic cell, comprises Copper Foil, and is coated on the active slurry layer of Copper Foil, and by quality percentage composition, the active slurry layer of above-mentioned lithium ion battery comprises 95.5% Delanium, 1.2%CMC, 2.8% butadiene-styrene rubber, 0.5% conductive carbon fibre.
A kind of polymer Li-ion battery, its preparation method comprises the following steps:
(1), the preparation of positive plate, by LiMn
1/3co
1/3ni
1/3o
2, conductive black, Kynoar and 1-METHYLPYRROLIDONE in mass ratio 100:2.5:3.5:47 stir into slurry, be coated on the aluminium foil of 20 micron thick, through 100 DEG C of oven dry, roll to 100 micron thick itemize, make positive plate, at aluminum lead of surface soldered of positive plate;
(2), negative plate adopts the anode plate for lithium ionic cell of the present embodiment; At nickel down-lead of surface soldered of negative plate;
(3), electrolyte: by electrolytic salt LiPF
6, being dissolved in volume ratio is in ternary organic solvent ethylene carbonate, dimethyl carbonate and the diethyl carbonate of 1:1:1, makes the electrolyte that concentration is 1mol/L;
(4), positive and negative plate and porous-gel composite polymer electrolyte membrane are wound into battery, dry through pack, edge sealing, baking, inject the operations such as electrolyte, vacuum heat-seal and polymerization, prepare polymer Li-ion battery.
Embodiment 2
20g sodium carboxymethylcellulose (CMC) is joined in 930g water, be stirred to dissolving, add 50g isopropyl alcohol, mix, obtain CMC mother liquor, wherein the solid content of CMC mother liquor is that 2wt%, viscosity are 8500mPas.
Get the above-mentioned CMC mother liquor of 1000g, add 10g electrically conductive graphite, 1940g native graphite, 30g polyvinyl alcohol, stirs, and obtains slurry, and wherein, the solid content of slurry is that 50wt%, viscosity are 5000mPas.
Get 1000g slurry and coat on Copper Foil, at 101 DEG C, dry, obtain anode plate for lithium ionic cell.
Above-mentioned anode plate for lithium ionic cell, comprises Copper Foil, and is coated on the active slurry layer of Copper Foil, and by quality percentage composition, the active slurry layer of above-mentioned lithium ion battery comprises 97% native graphite, 1%CMC, 1.5% polytetrafluoroethylene, 0.5% electrically conductive graphite.
A kind of aluminum steel case lithium ion battery, negative pole adopts the anode plate for lithium ionic cell of the present embodiment, utilizes the conventional preparation method in this area to prepare aluminum steel case lithium ion battery.
Embodiment 3
30g sodium carboxymethylcellulose (CMC) is joined in 2395g water, be stirred to dissolving, add 75g n-butanol and alcohol mixture (mass ratio of n-butanol and alcohol mixture is 1:1), mix, obtain CMC mother liquor, wherein, the solid content of described CMC mother liquor is that 1.2wt%, viscosity are 2000mPas.
Get the above-mentioned CMC mother liquor of 3750g, add 10g carbon nano-tube, 1960g carbonaceous mesophase spherules, 40g polyvinyl alcohol, stirs, and obtains slurry, and wherein, the solid content of described slurry is that 40wt%, viscosity are 3500mPas.
Get 2000g slurry and coat on Copper Foil, at 120 DEG C, dry, obtain anode plate for lithium ionic cell.
Above-mentioned anode plate for lithium ionic cell comprises Copper Foil, and is coated on the active slurry layer of Copper Foil, and by quality percentage composition, the active slurry layer of above-mentioned lithium ion battery comprises 96% carbonaceous mesophase spherules, 1.5%CMC, 2.0% polyvinyl alcohol, 0.5% carbon nano-tube.
A kind of polymer Li-ion battery, negative pole adopts the anode plate for lithium ionic cell of the present embodiment, utilizes the conventional preparation method in this area to prepare polymer Li-ion battery.
Embodiment 4
24g sodium carboxymethylcellulose (CMC) is joined in 1516g water, be stirred to dissolving, add the mixture (mass ratio of n-butanol, ethanol and acetone is 1:1:1) of 60g n-butanol, ethanol and acetone, mix, obtain CMC mother liquor, wherein, the solid content of described CMC mother liquor is that 1.5wt%, viscosity are 5000mPas.
Get the above-mentioned CMC mother liquor of 1600g, add the mixture (mass ratio of conductive carbon fibre and electrically conductive graphite is 1:1) of 10g conductive carbon fibre and electrically conductive graphite, the mixture (mass ratio of Delanium and native graphite is 7:3) of 1920g Delanium and native graphite, 44g polyvinyl alcohol, stir, obtain slurry, wherein, the solid content of institute's slurry is that 45wt%, viscosity are 5000mPas.
Get 2000g slurry and coat on Copper Foil, at 120 DEG C, dry, obtain anode plate for lithium ionic cell.
Above-mentioned anode plate for lithium ionic cell comprises Copper Foil, and be coated on the active slurry layer of Copper Foil, by quality percentage composition, the active slurry layer of above-mentioned lithium ion battery comprises the mixture of mixture, 1.2%CMC, 2.2% butadiene-styrene rubber, 0.5% conductive carbon fibre and the electrically conductive graphite of 96.1% Delanium and native graphite.
A kind of liquid soft-package battery, negative pole adopts the anode plate for lithium ionic cell of the present embodiment, utilizes the conventional preparation method in this area to prepare liquid soft-package battery.
Comparative example
A kind of polymer Li-ion battery, does not add pore creating material in the manufacture method of its negative plate, and other steps are with embodiment 1.
Polymer Li-ion battery to embodiment 1 and the lithium ion battery of comparative example carry out cycle performance test, and test condition is: at ambient temperature 15-35 DEG C, under the condition of humidity 45%-75%RH, between 3.0-4.2V, 0.5C discharges and recharges, and circulate 265 weeks.Test result as shown in Figure 2.
As seen from Figure 2, the polymer Li-ion battery of comparative example is after 265 charge and discharge cycles, and battery capacity drops to 85% left and right, and the battery capacity of the polymer Li-ion battery of embodiment 1 still reaches more than 90%.Visible, the useful life of the polymer Li-ion battery of embodiment 1 is compared with the length of comparative example.
The discharge performance under different multiplying of the polymer Li-ion battery of test implementation example 1 and comparative example lithium ion battery.Test condition is: at ambient temperature 15-35 DEG C, under the condition of humidity 45%-75%RH, while being 1. charged to 4.2V with 1C, change constant voltage charge into until electric current is less than or equal to 0.01C; 2. shelve after 5 minutes, with 0.2C current discharge to 3.0V, then with 1., 2. two steps circulation 2 times, record discharge capacity.3., while being charged to 4.2V with 1C, change constant voltage charge into until electric current is less than or equal to 0.01C; 2. shelve after 5 minutes, respectively with 1C, 0.2C, 0.5C, 2C current discharge to 3.0V, record discharge capacity.
Test result is shown in Table 1:
The polymer Li-ion battery of table 1 embodiment 1 and comparative example polymer Li-ion battery different multiplying are put
Electrical property contrast table
| ? | Embodiment 1 | Comparative example |
| Numbering | 28# | 30# |
| Initial capacity/mAh | 2544 | 2548 |
| 0.2C discharge capacity/mAh | 2545 | 2549 |
| 0.5C discharge capacity/mAh | 2608 | 2588 |
| 1C discharge capacity/mAh | 2585 | 2575 |
| 2C discharge capacity/mAh | 2563 | 2421 |
| 0.2C discharge capacity ratio % | 100% | 100% |
| 0.5C discharge capacity ratio % | 102.5% | 101.6% |
| 1C discharge capacity ratio % | 101.6% | 101.1% |
| 2C discharge capacity ratio % | 100.7% | 95% |
As shown in Table 1, the polymer Li-ion battery of embodiment 1 at the ratio of 0.5C-2C discharge capacity all higher than the polymer Li-ion battery of comparative example.
The discharge performance under low temperature (20 DEG C) of the polymer Li-ion battery of test implementation example 1 and comparative example lithium ion battery.Method of testing is: under the condition of 15-35 DEG C, 1. with 1C constant current charge, 4.2V constant voltage charge is to reaching termination electric current; 2. battery in the following order and condition test discharge performance, all charges to 4.2V before each test, and testing sequence is: (1) 25 ± 5 DEG C of insulation 2 hours, discharges into 3.0V with 1C; (2)-20 ± 2 DEG C are incubated 2 hours, are discharged to 3.0V with 0.5C.
Test result is shown in Table 2:
The polymer Li-ion battery of table 2 embodiment 1 and comparative example polymer Li-ion battery discharge performance contrast table at-20 DEG C
As shown in Table 2, the discharge capacity ratio of the polymer Li-ion battery of embodiment 1 in the time of low temperature is all higher than the polymer Li-ion battery of comparative example.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an anode plate for lithium ionic cell, comprises collector, and coats the active slurry layer of described collector, it is characterized in that, is formed with the hole that pore creating material forms in the time overflowing on described active slurry layer;
Described active slurry layer comprises the negative active core-shell material of routine by mass percentage 88-98%, thickener, the binding agent of 1.0-5% and the conductive agent of 0.5-2.0% of 0.5-5%.
2. anode plate for lithium ionic cell according to claim 1, it is characterized in that, described negative active core-shell material is selected from least one in carbon negative pole material, silicon based anode material and tin base cathode material, described thickener is sodium carboxymethylcellulose, described binding agent is polyvinyl alcohol or butadiene-styrene rubber, and described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube, Graphene, acetylene black, carbonaceous mesophase spherules and Ketjen black.
3. anode plate for lithium ionic cell according to claim 2, it is characterized in that, described negative active core-shell material is selected from least one in native graphite, Delanium and carbonaceous mesophase spherules, and described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube and Graphene.
4. a preparation method for anode plate for lithium ionic cell, is characterized in that, comprises the following steps:
Thickener is dissolved in solvent, adds pore creating material, mix, obtain thickener mother liquor, wherein, in described thickener mother liquor, the mass percent of described thickener is 0.5-10%, and the mass percent of described pore creating material is 1-10%;
In described thickener mother liquor, add conductive agent, negative active core-shell material and binding agent, stir, obtain active slurry;
Described active slurry is coated to collector, after dry, form the active slurry layer covering on described collector, obtain anode plate for lithium ionic cell, wherein, in described active slurry layer, the mass percent of described negative active core-shell material is 88-98%, and the mass fraction of described thickener is 0.5-5%, the mass percent of described binding agent is 1.0-5%, and the mass percent of described conductive agent is 0.5-2.0%.
5. the preparation method of anode plate for lithium ionic cell according to claim 4, is characterized in that, obtains being operating as of anode plate for lithium ionic cell after described being dried:
At 90-120 DEG C, the collector that is coated with described active slurry is dried, obtain described anode plate for lithium ionic cell.
6. the preparation method of anode plate for lithium ionic cell according to claim 4, is characterized in that, described pore creating material is selected from least one in n-butanol, isopropyl alcohol, ethanol and acetone.
7. the preparation method of anode plate for lithium ionic cell according to claim 4, is characterized in that, in described thickener mother liquor, the mass percent of described thickener is 1-2%, and the mass percent of described pore creating material is 1-5%.
8. the preparation method of anode plate for lithium ionic cell according to claim 4, it is characterized in that, in described active slurry layer, the mass percent of described negative active core-shell material is 95.5-97%, the mass fraction of described thickener is 1.2-2.5%, the mass percent of described binding agent is 1-2.8%, and the mass percent of described conductive agent is 0.5-2.0%.
9. the preparation method of anode plate for lithium ionic cell according to claim 4, it is characterized in that, described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube, Graphene, acetylene black, carbonaceous mesophase spherules and Ketjen black, and described negative active core-shell material is selected from least one in carbon negative pole material, silicon based anode material and tin base cathode material.
10. the preparation method of anode plate for lithium ionic cell according to claim 9, it is characterized in that, described conductive agent is selected from least one in conductive carbon fibre, electrically conductive graphite, carbon nano-tube and Graphene, and described negative active core-shell material is selected from least one in native graphite, Delanium and carbonaceous mesophase spherules.
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| PCT/CN2013/085445 WO2014183379A1 (en) | 2013-05-14 | 2013-10-18 | Lithium-ion battery negative plate and preparation method therefor |
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