CN101877394B - Lithium ion secondary battery cathode, preparation method thereof and lithium ion secondary battery - Google Patents
Lithium ion secondary battery cathode, preparation method thereof and lithium ion secondary battery Download PDFInfo
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- CN101877394B CN101877394B CN2009100505433A CN200910050543A CN101877394B CN 101877394 B CN101877394 B CN 101877394B CN 2009100505433 A CN2009100505433 A CN 2009100505433A CN 200910050543 A CN200910050543 A CN 200910050543A CN 101877394 B CN101877394 B CN 101877394B
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Abstract
The invention belongs to the field of lithium ion secondary batteries and provides a lithium ion secondary battery cathode which comprises cathode current collectors and silicon films deposited on the surface of the cathode current collectors, wherein the amount of the current collectors is two, each current collector is provided with a via hole, and the silicon films are deposited on the two surfaces of each current collector, at least one layer of the silicon film is provided with the via hole, and the average pore size of the via hole on the silicon film is 0.2-0.6mm; and the cathode current collectors are mutually overlaid, and at least one layer of silicon film is deposited on the adjacent surfaces of every two overlaying cathode current collectors. The lithium ion secondary battery cathode is adopted to overcome the defect of poor circulation performance of a battery when the silicon films are used as cathode active substances to greatly enhance the circulation performance of the battery under the room temperature: under the room temperature, the capacity retention can reach 100 percent after 200 charging and discharging circulations, and the capacity of the battery is increased less than the initial discharging capacity after 200-500 circulations.
Description
Technical field
The present invention relates to a kind of lithium ion secondary battery negative pole, its preparation method and the lithium rechargeable battery that comprises this negative pole.
Background technology
Silicon materials are because its lithium storage content (theoretical capacity 4200mAh/g) much larger than graphite-like material with carbon element (theoretical specific capacity 372mAh/g), becomes one of research focus of high-capacity lithium-ion secondary battery cathode material.Yet, because in the charge and discharge cycles process, the reversible generation of Li-Si alloy is accompanied by huge change in volume with decomposition, can cause the mechanical disintegration (producing crack and efflorescence) of alloy, cause the avalanche of material structure and peeling off of electrode material and electrode material lost electrically contacting, cause the cycle performance of electrode sharply to descend, cause electrode failure at last.Therefore, silicon materials are difficult to practical application in lithium rechargeable battery.
Summary of the invention
When being used for lithium ion secondary battery negative pole in order to solve silicon materials, the technical problem that cycle performance of battery is relatively poor, the present invention at first provides a kind of lithium ion secondary battery negative pole, comprise negative current collector and be deposited on the lip-deep silicon thin film of negative current collector, at least 2 of the numbers of negative current collector, through hole is all arranged on each negative current collector, all deposit silicon thin film on 2 surfaces of each negative current collector, and on one deck silicon thin film through hole is arranged at least, the average pore size of through hole is 0.2～0.6mm on the silicon thin film; Negative current collector is stacked mutually, and deposits at least 1 layer of silicon thin film on the adjacently situated surfaces of per 2 mutual stacked negative current collectors.
In order to prepare above-mentioned lithium ion secondary battery negative pole, the present invention and then a kind of preparation method of lithium ion secondary battery negative pole is provided, be included in depositing silicon film on the negative current collector, cleaning silicon thin film and negative current collector, drying, at each negative current collector through hole is set, and at one deck silicon thin film at least through hole is set, the average pore size of through hole is 0.2～0.6mm on the silicon thin film, then surface deposition is had the negative current collector of silicon thin film stacked mutually, makes lithium ion secondary battery negative pole.
When being used for lithium ion secondary battery negative pole in order to solve silicon materials, the technical problem that cycle performance of battery is relatively poor, the present invention provides a kind of lithium rechargeable battery at last, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, and described negative pole is lithium ion secondary battery negative pole of the present invention.
Beneficial effect of the present invention: lithium ion secondary battery negative pole provided by the invention adopts and comprises negative current collector and be deposited on the lip-deep silicon thin film of negative current collector, at least 2 of the numbers of negative current collector, through hole is all arranged on each negative current collector, all deposit silicon thin film on 2 surfaces of each negative current collector; Negative current collector is stacked mutually, and deposit the structure of at least 1 layer of silicon thin film on the adjacently situated surfaces of per 2 mutual stacked negative current collectors, the essence of this structure be utilize the multilayer silicon membrane layer to stack to put to alleviate can the charge and discharge cycles process in, the volumetric expansion of silicon materials, thereby better solve because the problem of the cycle performance of battery difference that the volumetric expansion of silicon materials causes, so cycle performance of battery is greatly improved, battery capacity slightly increased than initial discharge capacity after capability retention can reach 100%, 200～500 circulations after following 200 charge and discharge cycles of normal temperature.
Description of drawings
First kind of lithium ion secondary battery negative pole structural representation of Fig. 1 specific embodiment of the invention
Second kind of lithium ion secondary battery negative pole structural representation of Fig. 2 specific embodiment of the invention
The third lithium ion secondary battery negative pole structural representation of Fig. 3 specific embodiment of the invention
Cycle performance test result under the lithium rechargeable battery normal temperature of Fig. 4 embodiment of the invention 1
Cycle performance test result under the lithium rechargeable battery normal temperature of Fig. 5 embodiment of the invention 2
Embodiment
Describe the present invention below in detail.
The specific embodiment of the invention at first provides a kind of lithium ion secondary battery negative pole, comprise negative current collector and be deposited on the lip-deep silicon thin film of negative current collector, at least 2 of the numbers of negative current collector, through hole is all arranged on each negative current collector, all deposit silicon thin film on 2 surfaces of each negative current collector; Negative current collector is stacked mutually, and deposits at least 1 layer of silicon thin film on the adjacently situated surfaces of per 2 mutual stacked negative current collectors.
The structure of above-mentioned lithium ion secondary battery negative pole similar " sandwich " namely deposits at least 1 layer of silicon thin film on the adjacently situated surfaces of per 2 mutual stacked negative current collectors, is example as depicted in figs. 1 and 2.The stacked structure of this multilayer silicon thin film can effectively play in the buffering charge and discharge process, the effect of silicon materials volumetric expansion, thereby the cycle performance of raising battery.All through hole to be arranged on each negative current collector, otherwise, lithium ion (Li
+) directed mobile under the effect of electric field between the positive and negative electrode, easily form Li
+The enrichment of a certain position makes Li in battery
+Be difficult between positive and negative electrode, embed normally and deviate from, thereby the charge and discharge cycles of battery is difficult to normally carry out.
The number of plies of the silicon thin film that deposits on the adjacently situated surfaces of per 2 mutual stacked negative current collectors can be identical, also can be different; The thickness of every layer of silicon thin film can be identical, also can be different.
Comprise 2 negative current collector a and b with the lithium ion secondary battery negative pole that Figure 1 shows that example, wherein, surperficial a2 of a is adjacent with the surperficial b1 of b.The thick silicon thin film of the last deposition of a1 one deck 3 μ m, the thick silicon thin film of the last deposition of a2 one deck 2 μ m; The two-layer silicon thin film of the last deposition of b1, thickness is respectively 2 μ m, 3 μ m, the thick silicon thin film of the last deposition of b2 one deck 2 μ m.
The number of plies of the silicon thin film that deposits on the adjacently situated surfaces of preferred per 2 mutual stacked negative current collectors and every layer thickness all equate.Comprise 2 negative current collector c and d with the lithium ion secondary battery negative pole that Figure 2 shows that example, wherein, surperficial c2 of c is relative with the surperficial d1 of d.The thick silicon thin film of the last deposition of c1 one deck 3 μ m, the thick silicon thin film of the last deposition of c2 one deck 2 μ m; Respectively deposit the thick silicon thin film of one deck 2 μ m on d1, the d2.
More preferably the number of plies of each surperficial upward silicon thin film of deposition of all negative current collectors and every layer thickness all equate.Comprise 3 negative current collector x, y, z with the lithium ion secondary battery negative pole that Figure 3 shows that example, wherein, surperficial x2 of x is relative with the surperficial y1 of y, and the surperficial y2 of another of y is relative with the surperficial z1 of z.Two surperficial x1, the x2 of x, two surperficial y1, the y2 of y all deposit the thick silicon thin film of one deck 3 μ m on two surperficial z1, the z2 of z.
The number of plies of the silicon thin film that deposits on the adjacent surface of per 2 mutual stacked negative current collectors or every layer thickness not simultaneously, the asymmetric change in volume of silicon thin film can cause the active material split layer in the battery charge and discharge process, this can cause the loss of part capacity.So the number of plies of the silicon thin film that deposits on the adjacently situated surfaces of preferred per 2 mutual stacked negative current collectors and every layer thickness all equates, more preferably the number of plies of silicon thin film of deposition is gone up and every layer thickness all equates in each surface of all negative current collectors.
The thickness of the gross thickness of silicon thin film and monolayer silicon film is to the cycle life of the negative pole that comprises silicon, and then the cycle life of battery is all had certain influence.The silicon thin film gross thickness is unnecessary too greatly, and is not obvious to the cushioning effect of silicon materials volumetric expansion, and can increase the internal resistance of cell; Gross thickness is thin excessively, and when namely electrode active material content was too low, its storage lithium amount was too low, makes the capacity of battery and the standard that cycle performance all is difficult to reach practical application.The inventor discovers that the gross thickness of described silicon thin film preferably is no more than 20 μ m; Further preferably, be no more than under the prerequisite of 20 μ m thickness 1～10 μ m of monolayer silicon film in gross thickness.
Silicon thin film can be crystal silicon thin film, also can be amorphous silicon membrane, and when adopting amorphous silicon membrane, the cycle performance of battery is better, so, preferred amorphous silicon membrane.
There is through hole can improve electrolyte to the wettability of silicon thin film on the one hand on the silicon thin film, also can plays the effect of buffering silicon materials volumetric expansion on the other hand.So, preferably on one deck silicon thin film through hole is arranged at least.
The inventor discovers that further the average pore size of through hole is when 0.2～0.6mm on the silicon thin film, and electrolyte is all better to the buffering of silicon thin film volumetric expansion to wettability and the through hole of silicon thin film, and corresponding, cycle performance of battery obtains bigger raising.So the average pore size of through hole is 0.2～0.6mm on the preferred silicon thin film.
Preferred 1～15 the hole/mm of the average hole density of through hole on the described silicon thin film of one deck at least
2
The preparation method of through hole is not particularly limited on the described silicon thin film, can select one of following two kinds.Method one: use physical vaporous deposition earlier, for example electron beam evaporation plating, RF sputter plating etc. make pulverous silicon deposit in the negative pole currect collecting surface, form one deck silicon thin film, repeat this operation, can form the multilayer silicon thin film in the negative pole currect collecting surface.Then, there is the negative pole currect collecting body and function perforating device of silicon thin film to punch surface deposition, like this, on silicon thin film and the negative current collector through hole arranged.The specific embodiment of the invention adopts the laser drilling device punching, during laser drilling, if in air, operate, then on the silicon thin film near the silicon the through hole to have part oxidized.The inventor finds, when punching according to the average pore size of the through hole of the specific embodiment of the invention and average hole density, the oxide of Si (may be SiO
2) account for described silicon thin film the quality percentage composition very little, be no more than 10wt%, can the quality of silicon thin film not impacted, thereby can the cycle performance of battery not exerted an influence yet.Adopt earlier at collection liquid surface depositing silicon film, during again to the method for the collector laser drilling that deposited silicon thin film, be preferably in vacuum, or the inert gas with pasc reaction is arranged not, for example carry out under the protection of argon gas.
Method two: earlier get through hole with perforating device at negative current collector, then according to method one at negative current collector surface deposition silicon thin film.The silicon thin film that obtains so generally also has through hole at the lead to the hole site place of negative current collector, and the clear size of opening of silicon thin film is generally less than the through hole of negative current collector.Also can there be the position of through hole to continue evaporation at silicon thin film, obtains not having the silicon thin film of through hole.
The method that forms silicon thin film in the negative pole currect collecting surface does not have particular restriction, can adopt this area physical vaporous deposition commonly used, and concrete example comprises electron beam evaporation plating, RF sputter plating etc.Generally speaking, when adopting physical vaporous deposition, vacuum degree should be more high more good.It is high that but the too high one side of vacuum degree requires equipment, and sedimentation time is long on the other hand, thus generally do not use too high vacuum degree, but can not be too low, in order to avoid generate the purity of more impurity effect silicon thin film.Generally, the vacuum degree during physical vapour deposition (PVD) should be controlled at 0.02～2 millitorr.
The charge-discharge performance of the lithium rechargeable battery that the surface roughness anticathode of negative current collector is siliceous is influential.When the surface roughness of negative current collector was big, the effect that reduces silicon fiml volumetric expansion in the battery charge and discharge process was better, thereby cycle performance of battery improves bigger; But when surface roughness was too big, it was relatively poor to have deposited the negative plate surface gloss behind the silicon thin film, and cycle performance of battery is affected.Surface roughness is too little, and then silicon fiml adhesive force is low, can cause the material that falls in the cyclic process.The inventor finds, the surface roughness R of negative current collector
ZWhen 0.5～5 mu m range, the cycle performance of battery is better.So, the surface roughness R of preferred negative current collector
ZBe 0.5～5 μ m.
A kind of preparation method of lithium ion secondary battery negative pole sheet, be included in depositing silicon film on the negative current collector, cleaning silicon thin film and negative current collector, drying, then surface deposition there is the negative current collector of silicon thin film stacked mutually, makes lithium ion secondary battery negative pole.
Cleaning is for flush away because the impurity that the touch of staff stays at silicon film surface, so can select polar organic solvent for use, for example cleaning such as ethanol, acetone.
A kind of lithium rechargeable battery, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole the lithium ion secondary battery negative pole that described negative pole provides for the specific embodiment of the invention successively.
Because the negative pole of battery has at least 2 negative current collectors, so, each negative current collector all can be drawn one or several negative electrode lug, then all negative electrode lugs are welded together, constitute the negative electrode lug of battery; Also surface deposition can there be the stacked back of several negative current collectors of silicon thin film with sheet metal each negative current collector is electrically connected (mode that for example adopts welding), sheet metal will guarantee good electrical connection between negative current collector, and then draws the negative electrode lug of battery at described sheet metal.The battery cathode ear set-up mode of the specific embodiment of the invention is not limited to above-mentioned 2 kinds, as long as can guarantee that in battery operated process, all negative current collectors can both normally play a role, all in protection scope of the present invention.
The positive active material of lithium rechargeable battery does not have specific (special) requirements, can select the positive active material used always, for example LiCoO
2, LiNiO
2, LiMn
2O
4, LiMnO
2Deng the transition metal oxide that contains lithium.The inventor finds, when positive active material is selected LiCoO for use
2The time, average grain diameter is at the LiCoO of 5～15 μ m
2Can make the cycle performance of battery better, so the positive active material of preferred lithium ion battery comprises that average grain diameter is at the LiCoO of 5～15 μ m
2
The composition of the electrolyte of lithium rechargeable battery does not have specific (special) requirements, can prepare according to this area prescription commonly used, for example, bath composition is preferably as follows: ethylene carbonate and diethyl carbonate are that solvent is made in 0.3～1 mixing by volume, and electrolytic salt comprises LiPF
6, concentration is 0.5～2mol/L.
The barrier film of lithium rechargeable battery and cell making process all do not have particular restriction, can carry out according to the state of the art.These property related to the present invention are little, so do not repeat them here.
Embodiment 1
1. the making of negative pole
1.1 deposition of amorphous silicon films:
Select the Copper Foil of 3 same sizes as negative current collector.The length and width of Copper Foil is respectively 480mm, 44mm, thick 15 μ m, and the two-sided roughness of Copper Foil is R
Z=2.5 μ m.With electron beam vapour deposition method (EB-PVD vacuum evaporation instrument), be raw material is 6 μ m at each evaporation 1 layer thickness of two surfaces of every Copper Foil silicon thin film with the silica flour (amorphous) of purity 99.99%.The silicon thin film that obtains is amorphous silicon membrane.The EB-PVD operating voltage is 7000V, and operating current is 120mA, and the vacuum chamber operating pressure is 0.05 millitorr.
1.2 amorphous silicon membrane punching:
The Copper Foil that 3 two surfaces that step 1.1 is obtained all deposit amorphous silicon membrane is stacked, and with the laser marking machine that BYD company oneself produces 3 Copper Foils that stack together is punched, and average pore size is 0.4mm, and average hole density is 2/mm
2
1.3 clean:
Earlier the surperficial 5min of the negative current collector that obtains with absolute ethyl alcohol cleaning step 1.2 uses washed with de-ionized water 5min then.
1.4 dry:
The negative current collector that step 1.3 is obtained placed clean 150 ℃ of dryings of vacuum drying chamber 2 hours, finished the making of lithium ion secondary battery negative pole sheet.The negative plate structure is similar to Fig. 3, just the thickness difference of individual layer amorphous silicon membrane.
2. Zheng Ji making
With positive active material LiCoO
2(granularity 10 μ m) 100g, aqueous solvent 80g, conductive agent acetylene black 3g, bonding agent 3g (each 1.5g of CMC and SBR) mixes and makes anode sizing agent, is coated on two surfaces of aluminium foil (plus plate current-collecting body) of length and width, the thick 485mm of being respectively, 45mm, 8 μ m with coating machine then.The positive plate of length * wide * thick=480mm * 45mm * 12mm is cut in 70 ℃ of vacuumize 2 hours then.Positive active material LiCoO on the every positive plate
2Content be 10g.
3. the making of electrolyte
Be to be mixed into mixed solvent at 3: 7 by volume with ethylene carbonate and diethyl carbonate, (ethylene carbonate 3ml, diethyl carbonate 7ml) is with electrolytic salt LiPF
6Join in the above-mentioned mixed solvent, the concentration of electrolytic salt is 1mol/L.
4. the making of lithium rechargeable battery
With above-mentioned positive and negative electrode pole piece respectively with the electrode group of three layers of membrane coil coiled of polyethylene/polypropylene/polyethylene square lithium ion battery of thick 18 μ m, put into the square battery shell of 50mm * 34mm * 5mm then, in glove box, in ar gas environment, manually inject the about 6ml of above-mentioned electrolyte, lithium rechargeable battery is made in sealing.
After battery is made, according to actual discharge capacity and the normal-temperature circulating performance of following method test battery:
The volume test of battery actual discharge: the 120mA constant current charge is after 2 hours, and the 200mA constant current charge is to 4.0V, cut-off current 20mA, and 200mA is put into 3.0V then.
The test of battery normal-temperature circulating performance: 200mA is charged to 4.0V, cut-off current 20mA, and 200mA is put into 3.0V then.
The theoretical discharge capacity of cell negative electrode material is 1700mAh/g, and the actual discharge capacity of cell negative electrode material is 1200mAh/g, the design capacity C=1000mAh of battery.The about 600mAh of battery actual discharge capacity, following 200 the circulation back capability retentions 100% of normal temperature.The theoretical discharge capacity of cell negative electrode material=battery design capacity/negative material dressing amount, the actual discharge capacity of cell negative electrode material=battery actual discharge capacity/negative material dressing amount.The circulation volume conservation rate of battery as shown in Figure 4 under the normal temperature.
Embodiment 2
According to the method for embodiment 1, different is: negative current collector is the beraloy Copper Foil of thick 18 μ m, and number is 2, and its two-sided roughness equates, is R
Z=3.5 μ m; During electron beam evaporation plating, vacuum degree 0.08 millitorr; The every layer of amorphous silicon membrane thickness that deposits on the negative pole currect collecting surface is 5 μ m; The average pore size of through hole is 0.2mm on the silicon thin film, and average hole density is 5/mm
2The negative plate structure that obtains is similar to Fig. 2, and just the thickness of the every layer of amorphous silicon membrane that deposits on the negative pole currect collecting surface is all identical, and is 5 μ m.
The theoretical discharge capacity of cell negative electrode material is 950mAh/g, and the actual discharge capacity of cell negative electrode material is 680mAh/g, the design capacity C=700mAh of battery, actual discharge capacity 620mAh, following 200 the circulation back capability retentions 100% of normal temperature.
The inventor also finds, among the embodiment 1 and 2, proceeds in the process of charge and discharge cycles after 200 circulations, and battery capacity has a certain amount of increase, and after 500 circulations, discharge capacity of the cell is kept constant greatly, substantially no longer changes.This may be since silicon to Li
+The reason that slow-release function is arranged.The circulation volume conservation rate of battery as shown in Figure 5 under the normal temperature.
Comparative Examples 1
Selecting length and width is respectively 480mm, 44mm, and thick 15 μ m, two-sided coarse Copper Foil are as negative current collector, and the two-sided roughness of Copper Foil is R
Z=2.5 μ m.With electron beam vapour deposition method (EB-PVD vacuum evaporation instrument), silica flour (amorphous) with purity 99.99% is that raw material is the silicon thin film (method of prior art) of 3 μ m at each evaporation 1 layer thickness of two surfaces of Copper Foil, then according to operation cleaning, the drying of embodiment 1, obtain respectively depositing on 2 surfaces of negative current collector the negative plate of one deck amorphous silicon membrane.Different with embodiment is that the negative current collector of Comparative Examples has only 1.
With reference to the method for embodiment 1, use this negative plate to be assembled into lithium rechargeable battery, and its performance is tested, the result is as follows:
The design capacity C=700mAh of battery, actual discharge capacity 350mAh, following 200 the circulation back capability retentions 80% of normal temperature.
By comparing embodiment and Comparative Examples as can be seen:
1. the lithium rechargeable battery normal-temperature circulating performance that provides of the embodiment of the invention is better: capability retention can reach 100% after following 200 charge and discharge cycles of normal temperature, improves 15～20% than prior art.
2. two surfaces of Copper Foil have respectively deposited the amorphous silicon membrane of 1 layer of 3 μ m in the Comparative Examples, and respectively deposited 3 layers of amorphous silicon membrane on two of Copper Foil surfaces in embodiment 1 and 2, monolayer film thickness is respectively 6 μ m and 5 μ m, all big than Comparative Examples, and the battery normal-temperature circulating performance of embodiment is better than Comparative Examples, and this result is opposite with a kind of viewpoint of prior art.This viewpoint of prior art is: the amorphous silicon membrane that lithium ion battery negative uses micron order thickness is during as negative electrode active material, and along with the increase of silicon thin film thickness, cycle performance of battery descends.
The chemical raw material of using in the embodiment of the invention, tester are respectively shown in following table 1, table 2.
Table 1: embodiment of the invention agents useful for same and raw material
| Chemical reagent/raw material | Purity/model | The source |
| LiCoO 2 | LITHIUM BATTERY | Umicore (Umicore) |
| Copper Foil | - | Plum wild goose electrolytic copper foil Co., Ltd |
| Silica flour | 0.9999 | Shenzhen TGT company |
Table 2: the used various method of testings of the embodiment of the invention and instrument
| The instrument title | The place of production, model |
| Blue electric battery test system | The blue electricity in Wuhan, CT2001A |
| EB-PVD evaporation instrument | Beijing Beiyi Innovation Vacuum Technology Co., Ltd., 800 vacuum coating equipments |
| Scanning electron microscopy | Japan JEOL |
| X-ray energy spectrometer | U.S. NORAN, JSM-5610LV |
| X-ray powder diffraction instrument | Japan (Rigaku) of science, D/max2000PC |
| The punching machine | The self-produced laser marking machine of BYD |
Claims (10)
1. lithium ion secondary battery negative pole, comprise negative current collector and be deposited on the lip-deep silicon thin film of negative current collector, it is characterized in that at least 2 of the numbers of negative current collector, through hole is all arranged on each negative current collector, all deposit silicon thin film on 2 surfaces of each negative current collector; Negative current collector is stacked mutually, and deposits at least 1 layer of silicon thin film on the adjacently situated surfaces of per 2 mutual stacked negative current collectors, and on one deck silicon thin film through hole is arranged at least, and the average pore size of through hole is 0.2～0.6mm on the silicon thin film.
2. according to the lithium ion secondary battery negative pole of claim 1, it is characterized in that the number of plies of the silicon thin film that deposits on the adjacently situated surfaces of per 2 mutual stacked negative current collectors and every layer thickness all equate.
3. according to the lithium ion secondary battery negative pole of claim 2, it is characterized in that the number of plies of the silicon thin film that deposits is gone up on each surface of all negative current collectors and every layer thickness all equates.
4. according to the lithium ion secondary battery negative pole of claim 1, it is characterized in that the gross thickness of the silicon thin film that deposits on the adjacently situated surfaces of per 2 mutual stacked negative current collectors is no more than 20 μ m.
5. according to the lithium ion secondary battery negative pole of claim 4, it is characterized in that every layer of silicon thin film thickness 1～10 μ m.
6. according to the lithium ion secondary battery negative pole of claim 1, it is characterized in that described silicon thin film is amorphous silicon membrane.
7. according to the lithium ion secondary battery negative pole of claim 1, it is characterized in that the average hole density of through hole is 1～15 hole/mm on the silicon thin film
2
8. according to the lithium ion secondary battery negative pole of claim 1, it is characterized in that the surface roughness R of described negative current collector
ZBe 0.5～5 μ m.
9. the preparation method of lithium ion secondary battery negative pole according to claim 1, be included in depositing silicon film on the negative current collector, cleaning silicon thin film and negative current collector, drying, at each negative current collector through hole is set, and at one deck silicon thin film at least through hole is set, the average pore size of through hole is 0.2～0.6mm on the silicon thin film, then surface deposition there is the negative current collector of silicon thin film stacked mutually, makes the lithium ion secondary battery negative pole sheet.
10. lithium rechargeable battery, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, it is characterized in that described negative pole is lithium ion secondary battery negative pole according to claim 1.
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| CN102820451A (en) * | 2012-07-23 | 2012-12-12 | 深圳市海太阳实业有限公司 | Negative electrode pole piece and preparation method thereof, and lithium ion battery and preparation method thereof |
| CN104091921A (en) * | 2014-07-22 | 2014-10-08 | 厦门首能科技有限公司 | Porous silicon and carbon mixed anode plate and lithium ion secondary battery comprising same |
| CN105244471A (en) * | 2015-11-13 | 2016-01-13 | 力神动力电池系统有限公司 | Lithium ion battery electrode |
| WO2017094381A1 (en) * | 2015-12-03 | 2017-06-08 | ソニー株式会社 | Secondary battery, battery pack, electric vehicle, electrical energy storage system, electric tool and electronic device |
| CN109920978A (en) * | 2017-12-13 | 2019-06-21 | 上海杉杉科技有限公司 | A kind of high-capacity battery of the electrode of silica-base film containing rock-steady structure |
| CN110197895A (en) * | 2018-02-26 | 2019-09-03 | 华为技术有限公司 | A kind of composite material and preparation method |
| CN109062281A (en) * | 2018-08-17 | 2018-12-21 | 江苏芯界新能源科技有限公司 | A kind of negative electrode of lithium ion battery substrate and preparation method thereof |
| CN114883568A (en) * | 2022-06-29 | 2022-08-09 | 河南工业大学 | Negative electrode material, negative electrode plate containing negative electrode material, electrochemical device and electronic device |
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| JP5061433B2 (en) * | 2005-07-22 | 2012-10-31 | パナソニック株式会社 | Current collector and lithium ion secondary battery using the same |
| CN101132066B (en) * | 2006-08-25 | 2011-01-12 | 比亚迪股份有限公司 | Zinc cathode and secondary zinc-nickel battery with it and their manufacturing method |
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| CN1622380A (en) * | 2003-11-28 | 2005-06-01 | 松下电器产业株式会社 | Energy device and method for producing the same |
| CN101355147A (en) * | 2007-07-26 | 2009-01-28 | 索尼株式会社 | Cathode and battery |
| CN101394003A (en) * | 2007-09-18 | 2009-03-25 | 富士重工业株式会社 | Electric storage device |
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| JP特开2007-35297A 2007.02.08 |
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