CN103682366A - Aluminum foil/carbon composite current collector, preparation method of current collector and lithium ion battery - Google Patents

Aluminum foil/carbon composite current collector, preparation method of current collector and lithium ion battery Download PDF

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Publication number
CN103682366A
CN103682366A CN201210339618.1A CN201210339618A CN103682366A CN 103682366 A CN103682366 A CN 103682366A CN 201210339618 A CN201210339618 A CN 201210339618A CN 103682366 A CN103682366 A CN 103682366A
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aluminium foil
current collector
composite current
carbon composite
carbon
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CN103682366B (en
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周明杰
袁新生
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention relates to an aluminum foil/carbon composite current collector and a preparation method thereof. The preparation method comprises the following steps: (a) decontaminating and drying; (b) injecting ions; (c) corroding and drying. The invention also relates to a lithium ion battery which is prepared by using the aluminum foil/carbon composite current collector. According to the preparation method of the aluminum foil/carbon composite current collector and the lithium ion battery which is prepared by using the aluminum foil/carbon composite current collector, a carbon layer and the aluminum foil are embedded mutually and tightly bonded through ion injection, so that the natural transition between the carbon and the aluminum is realized; a contact inner resistance between the carbon layer and the aluminum foil is reduced; the performance of a carbon-aluminum composite layer is better than that a carbon-coated layer; the preparation process is simple; the cost is low; after corroding, an uneven surface is formed on the carbon-aluminum composite layer, so that a bonding force between a positive electrode material and the aluminum foil/carbon composite current collector can be increased; the cycle stability of the electrode can be improved; the service life of the electrode can be prolonged; after 1000 cycles, a capacity retention ratio can reach up to 97.1%.

Description

Aluminium foil/carbon composite current collector, its preparation method and lithium ion battery
Technical field
The present invention relates to electrochemical field, relate in particular to a kind of aluminium foil/carbon composite current collector and preparation method thereof.The invention still further relates to a kind of this aluminium foil/carbon composite current collector that adopts as the lithium ion battery of electrode material.
Background technology
At present lithium ion cell positive current collector material is generally selected aluminium foil, but contact resistance between aluminium foil and active material layer is excessive, and lithium ion with aluminium foil, embedding lithium can occur and react, and destruction aluminium foil, causes stability test and life-span reduction.So more conventional method is to reduce contact resistance at aluminium foil surface coated with conductive carbon-coating at present, but the combination between conductive coating and aluminium foil realizes by binding agent, and adhesion is strong not, and conductive carbon layer technology is grasped by Japanese minority enterprise, technical sophistication, cost is high.
Summary of the invention
The first goal of the invention of the present invention is to solve the problem and shortage that above-mentioned prior art exists, a kind of aluminium foil/carbon composite current collector and preparation method thereof is provided, by Implantation, carbon-coating and the aluminium foil of aluminium foil/carbon composite current collector are embedded mutually, realize the natural transition of carbon and aluminium, reduced the contact internal resistance of the two.
The second goal of the invention of the present invention is to provide a kind of lithium ion battery that adopts this aluminium foil/carbon composite current collector to prepare, to improve cyclical stability and the life-span of li-ion electrode, circulation 1000 times after capability retention can reach 97.1%.
For reaching the first goal of the invention of the present invention, the first technical scheme that the present invention adopts is: a kind of aluminium foil/carbon composite current collector and preparation method thereof, this preparation method comprises the steps:
(a) decontamination is dry: first by aluminium foil wipe oil dry;
(b) Implantation: by dried described aluminium foil, put into ion implantation device, pass into protective gas after sealing; utilize the method for high-speed ion injection, carbon is injected into the one side of described aluminium foil, obtain described aluminium foil/carbon composite current collector; wherein, Implantation amount is 1 * 10 -6～1 * 10 -4g/cm 2, injection length is 1～20 minute, Implantation Energy is 800～1500eV;
(c) corrosion is dry: after Implantation completes, take out described aluminium foil/carbon composite current collector, another side at described aluminium foil/carbon composite current collector is that nonionic injection face is smeared polymethyl methacrylate, after coating, described aluminium foil/carbon composite current collector is put into and in acid solution, carried out surface corrosion, after corrosion, use washed with de-ionized water erosional surface, until deionized water is neutral, then removes polymethyl methacrylate, and can use after described aluminium foil/carbon composite current collector is dry.
Described acid solution is a kind of in hydrochloric acid, nitric acid, sulfuric acid, and the concentration of described acid solution is 0.01～1mol/L.
In described step (a), be specially: with ethanol, acetone and deionized water, in described ultrasonic cleaning instrument, remove respectively the greasy dirt of described aluminium foil, and be dried 5～10 minutes in the vacuum drying chamber of 80～100 ℃.
In described step (b), described protective gas is a kind of in nitrogen, helium or argon gas.
In described step (c), the time that the Implantation face of described aluminium foil/carbon composite current collector is corroded is 10～300 minutes, and described aluminium foil/carbon composite current collector is dried to 10～24 hours in the vacuum drying chamber of 60～80 ℃.
For reaching the second goal of the invention of the present invention, the second technical scheme that the present invention adopts comprises the lithium ion battery obtaining according to the preparation method described in above any one, this lithium ion battery comprise by positive plate, barrier film, negative plate in order the stacked battery core forming, for installing the closed shell of described battery core, and filling is at the electrolyte of closed shell, described positive plate comprises collector and is coated in the positive electrode on this collector, and described collector adopts above-mentioned aluminium foil/carbon composite current collector.
Described positive electrode comprises the positive electrode active materials mixing at 85: 5: 10 in mass ratio, the acetylene black that plays the Kynoar of binding agent effect and play conductive agent effect, and described positive electrode active materials is LiFePO4, LiMn2O4 or cobalt acid lithium.
Solute in described electrolyte is LiPF 6, LiBF 4, LiTFSI (LiN (SO 2cF 3) 2), LiFSI (LiN (SO 2f) 2) in a kind of; Solvent in described electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile; Described solute in described electrolyte and the volume ratio of described solvent are 1: 1, and the concentration of described electrolyte is 1mol/L.
Compared with prior art, the preparation method of aluminium foil/carbon composite current collector of the present invention and the lithium ion battery that adopts this aluminium foil/carbon composite current collector to prepare, by Implantation, carbon-coating and aluminium foil are embedded mutually, in conjunction with tight, realize the natural transition of carbon and aluminium, be conducive to reduce the contact internal resistance of the two, make the performance of aluminium carbon composite layer be better than carbon coating, and preparation technology is simple, cost is low.Aluminium carbon composite layer produces rough surface after excessive erosion, also helps the adhesion that increases positive electrode and aluminium foil/carbon composite current collector, and cyclical stability and the life-span of raising electrode, the capability retention after 1000 times that circulates can reach 97.1%.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.
The preparation of aluminium foil/carbon composite current collector:
The preparation method of aluminium foil/carbon composite current collector of the present invention, roughly comprises the steps:
(a) decontamination is dry: first aluminium foil is removed respectively to the greasy dirt of aluminium foil in ultrasonic cleaning instrument with ethanol, acetone and deionized water, and be dried 5～10 minutes in the drying box of 80～100 ℃.The thickness of aluminium foil is generally conventional 9um, 12um, 16um (industry standard).
(b) Implantation: take out dried aluminium foil; put in ion implantation device; after good seal ion implantation device, pass into a kind of as protective gas in nitrogen, helium or argon gas; the method of utilizing high-speed ion to inject; carbon is injected into the one side of aluminium foil; obtain aluminium foil/carbon composite current collector, wherein, Implantation amount is 1 * 10 -6～1 * 10 -4g/cm 2, injection length is 1～20 minute, Implantation Energy is 800～1500eV;
(c) corrosion is dry: after Implantation completes, make described ion implantation device naturally cool to room temperature, take out aluminium foil/carbon composite current collector, another side at aluminium foil/carbon composite current collector is that nonionic injection face is smeared polymethyl methacrylate, after coating, aluminium foil/carbon composite current collector being put into concentration is in 0.01～1mol/L acid solution, Implantation face to aluminium foil/carbon composite current collector corrodes, the time that the Implantation face of aluminium foil/carbon composite current collector is corroded is 10～300 minutes, after corrosion, use washed with de-ionized water erosional surface, until deionized water is neutral, then remove polymethyl methacrylate, and aluminium foil/carbon composite current collector is placed in to the drying box of 60～80 ℃ after dry 10～24 hours, can uses.
Wherein, acid solution can be a kind of in hydrochloric acid, nitric acid, sulfuric acid.
The preparation of lithium ion battery:
The present invention also comprises the lithium ion battery of aluminium foil/carbon composite current collector of preparing containing said method, this lithium ion battery comprise positive plate, negative plate and be arranged on positive plate and negative plate between barrier film and electrolyte, positive plate is made by above-described aluminium foil/carbon composite current collector.
Below introduce the roughly step of using this aluminium foil/carbon composite current collector to be made into lithium ion battery:
(a) prepare battery anode slice:
The ratio that is 85: 5: 10 according to mass ratio, mixes positive electrode, Kynoar binding agent and conductive agent acetylene black, obtains slurry;
Then slurry is coated on aluminium foil/carbon composite current collector of preparing as 1～4 arbitrary embodiment, drying, rolls film, trimming and process, make based lithium-ion battery positive plate.
Wherein, positive electrode specifically can be: a kind of in LiFePO4, LiMn2O4, cobalt acid lithium.
(b) prepare battery cathode sheet:
The ratio that is 85: 5: 10 according to mass ratio, mixes graphite, butadiene-styrene rubber binding agent and conductive agent acetylene black, obtains slurry;
Afterwards slurry is coated on aluminium foil, drying, rolls film, trimming and process, make anode plate for lithium ionic cell.
(c) assembling of lithium ion battery:
By positive plate, barrier film, negative plate in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward injecting electrolyte by the liquid injection port being arranged on battery container in battery container, sealing liquid injection port, obtains lithium ion battery.
Wherein, the concentration of the electrolyte of lithium ion battery is generally 1mol/L, and the solute in electrolyte adopts the conventional electrolyte of lithium ion battery, as LiPF 6, LiBF 4, LiTFSI (LiN (SO 2cF 3) 2) and LiFSI (LiN (SO 2f) 2) etc., solvent is for adopting one or more mixing in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile, and solute and ratio of solvent are 1: 1.
In addition, barrier film can adopt U.S. celgard 2400 polypropylene porous films.
Preparation process with 1～4 pair of aluminium foil/carbon composite current collector of the present invention of embodiment is specifically described below:
Embodiment 1
In the embodiment of the present invention 1, the preparation method of aluminium foil/carbon composite current collector comprises the steps:
(a) decontamination is dry: first use respectively ethanol, acetone and deionized water ultrasonic in ultrasonic cleaning instrument on aluminium foil, wipe oil, is then placed in vacuum drying chamber and is dried 5 minutes in 80 ℃;
(b) Implantation: take out dried aluminium foil; put in ion implantation device; after good seal equipment, pass into nitrogen as protective gas; the method of utilizing high-speed ion to inject; carbon is injected into the one side of aluminium foil; obtain aluminium foil/carbon composite current collector, wherein, the amount of Implantation is 1 * 10 -6/ cm 2, injection length is 20 minutes, Implantation Energy is 800eV;
(c) corrosion is dry: after Implantation completes, make equipment naturally cool to room temperature, open lid, take out aluminium foil/carbon composite current collector, at another side, be that nonionic injection face is coated polymethyl methacrylate (english abbreviation is PMMA), anti-face is here corroded.After coating, aluminium foil/carbon composite current collector is put in the sulfuric acid solution of 0.01mol/L, Implantation face is corroded 300 minutes, after corrosion, use washed with de-ionized water erosional surface, until deionized water is neutral, then remove polymethyl methacrylate, and aluminium foil/carbon composite current collector is placed in the vacuum drying chamber of 60 ℃ dry 24 hours.
Embodiment 2
In the embodiment of the present invention 2, the preparation method of aluminium foil/carbon composite current collector comprises the steps:
(a) decontamination is dry: first use respectively ethanol, acetone and deionized water ultrasonic in ultrasonic cleaning instrument on aluminium foil, wipe oil, is then placed in vacuum drying chamber and is dried 5 minutes in 100 ℃;
(b) Implantation: take out dried aluminium foil; put in ion implantation device; after good seal equipment, pass into helium as protective gas; the method of utilizing high-speed ion to inject; carbon is injected into the one side of aluminium foil; obtain aluminium foil/carbon composite current collector, wherein, the amount of Implantation is 1 * 10 -4/ cm 2, injection length is 1 minute, Implantation Energy is 1500eV;
(c) corrosion is dry: after Implantation completes, make equipment naturally cool to room temperature, open lid, take out aluminium foil/carbon composite current collector, at another side, be that nonionic injection face is coated polymethyl methacrylate (english abbreviation is PMMA), anti-face is here corroded, after coating, aluminium foil/carbon composite current collector is put in the hydrochloric acid solution of 1mol/L, Implantation face is corroded 10 minutes, after corrosion, use washed with de-ionized water erosional surface, until deionized water is neutral, then remove polymethyl methacrylate, and aluminium foil/carbon composite current collector is placed in the vacuum drying chamber of 80 ℃ dry 10 hours, .
Embodiment 3
In the embodiment of the present invention 3, the preparation method of aluminium foil/carbon composite current collector comprises the steps:
(a) decontamination is dry: first use respectively ethanol, acetone and deionized water ultrasonic in ultrasonic cleaning instrument on aluminium foil, wipe oil, is then placed in vacuum drying chamber and is dried 8 minutes in 90 ℃;
(b) Implantation: take out dried aluminium foil; put in ion implantation device; after good seal equipment, pass into argon gas as protective gas; the method of utilizing high-speed ion to inject; carbon is injected into the one side of aluminium foil; obtain aluminium foil/carbon composite current collector, wherein, the amount of Implantation is 1 * 10 -5/ cm 2, injection length is 10 minutes, Implantation Energy is 1000eV;
(c) corrosion is dry: after Implantation completes, make equipment naturally cool to room temperature, open lid, take out aluminium foil/carbon composite current collector, at another side, be that nonionic injection face is coated polymethyl methacrylate (english abbreviation is PMMA), anti-face is here corroded, after coating, aluminium foil/carbon composite current collector is put in the salpeter solution of 0.1mol/L, Implantation face is corroded 30 minutes, after corrosion, use washed with de-ionized water erosional surface, until deionized water is neutral, then remove polymethyl methacrylate, and aluminium foil/carbon composite current collector is placed in the vacuum drying chamber of 80 ℃ dry 20 hours, .
Embodiment 4
In the embodiment of the present invention 4, the preparation method of aluminium foil/carbon composite current collector comprises the steps:
(a) decontamination is dry: first use respectively ethanol, acetone and deionized water ultrasonic in ultrasonic cleaning instrument on aluminium foil, wipe oil, is then placed in vacuum drying chamber and is dried 10 minutes in 85 ℃;
(b) Implantation: take out dried aluminium foil; put in ion implantation device; after good seal equipment, pass into nitrogen as protective gas; the method of utilizing high-speed ion to inject; carbon is injected into the one side of aluminium foil; obtain aluminium foil/carbon composite current collector, wherein, the amount of Implantation is 5 * 10 -5/ cm 2, injection length is 5 minutes, Implantation Energy is 1200eV;
(c) corrosion is dry: after Implantation completes, make equipment naturally cool to room temperature, open lid, take out aluminium foil/carbon composite current collector, at another side, be that nonionic injection face is coated polymethyl methacrylate (english abbreviation is PMMA), anti-face is here corroded, after coating, aluminium foil/carbon composite current collector is put in the hydrochloric acid solution of 0.5mol/L, Implantation face is corroded 20 minutes, after corrosion, use washed with de-ionized water erosional surface, until deionized water is neutral, then remove polymethyl methacrylate, and aluminium foil/carbon composite current collector is placed in the vacuum drying chamber of 70 ℃ dry 18 hours, .
Preparation process with 5～8 pairs of lithium ion batteries of the present invention of embodiment is specifically described below:
Embodiment 5
(a) prepare battery anode slice:
The ratio that is 85: 5: 10 according to mass ratio, mixes LiFePO4, Kynoar binding agent and conductive agent acetylene black, obtains slurry;
Then slurry is coated on aluminium foil/carbon composite current collector that embodiment 1 prepares, drying, roll film, trimming is processed, and makes based lithium-ion battery positive plate.
(b) prepare battery cathode sheet:
The ratio that is 85: 5: 10 according to mass ratio, mixes graphite, butadiene-styrene rubber binding agent and conductive agent acetylene black, obtains slurry;
Afterwards slurry is coated on aluminium foil, drying, rolls film, trimming and process, make anode plate for lithium ionic cell.
(c) assembling of lithium ion battery:
By positive plate, barrier film, negative plate in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward injecting electrolyte by the liquid injection port being arranged on battery container in battery container, sealing liquid injection port, obtains lithium ion battery.
That wherein the electrolyte of lithium ion battery is selected is the LiBF of 1mol/L 4/ diethyl carbonate, barrier film adopts U.S. celgard 2400 polypropylene porous films.
Embodiment 6
(a) prepare battery anode slice:
The ratio that is 85: 5: 10 according to mass ratio, mixes LiMn2O4, Kynoar binding agent and conductive agent acetylene black, obtains slurry;
Then slurry is coated on aluminium foil/carbon composite current collector that embodiment 2 prepares, drying, roll film, trimming is processed, and makes based lithium-ion battery positive plate.
(b) prepare battery cathode sheet:
The ratio that is 85: 5: 10 according to mass ratio, mixes graphite, butadiene-styrene rubber binding agent and conductive agent acetylene black, obtains slurry;
Afterwards slurry is coated on aluminium foil, drying, rolls film, trimming and process, make anode plate for lithium ionic cell.
(c) assembling of lithium ion battery:
By positive plate, barrier film, negative plate in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward injecting electrolyte by the liquid injection port being arranged on battery container in battery container, sealing liquid injection port, obtains lithium ion battery.
That wherein the electrolyte of lithium ion battery is selected is the LiPF of 1mol/L 6/ propene carbonate, barrier film adopts U.S. celgard 2400 polypropylene porous films.
Embodiment 7
(a) prepare battery anode slice:
The ratio that is 85: 5: 10 according to mass ratio, mixes cobalt acid lithium, Kynoar binding agent and conductive agent acetylene black, obtains slurry;
Then slurry is coated on aluminium foil/carbon composite current collector that embodiment 3 prepares, drying, roll film, trimming is processed, and makes based lithium-ion battery positive plate.
(b) prepare battery cathode sheet:
The ratio that is 85: 5: 10 according to mass ratio, mixes graphite, butadiene-styrene rubber binding agent and conductive agent acetylene black, obtains slurry;
Afterwards slurry is coated on aluminium foil, drying, rolls film, trimming and process, make anode plate for lithium ionic cell.
(c) assembling of lithium ion battery:
By positive plate, barrier film, negative plate in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward injecting electrolyte by the liquid injection port being arranged on battery container in battery container, sealing liquid injection port, obtains lithium ion battery.
Wherein, what the electrolyte of lithium ion battery was selected is LiFSI/ ethylene carbonate+acetonitrile of 1mol/L, and barrier film adopts U.S. celgard 2400 polypropylene porous films.
Embodiment 8
(a) prepare battery anode slice:
The ratio that is 85: 5: 10 according to mass ratio, mixes LiFePO4, Kynoar binding agent and conductive agent acetylene black, obtains slurry;
Then slurry is coated on aluminium foil/carbon composite current collector that embodiment 4 prepares, drying, roll film, trimming is processed, and makes based lithium-ion battery positive plate.
(b) prepare battery cathode sheet:
The ratio that is 85: 5: 10 according to mass ratio, mixes graphite, butadiene-styrene rubber binding agent and conductive agent acetylene black, obtains slurry;
Afterwards slurry is coated on aluminium foil, drying, rolls film, trimming and process, make anode plate for lithium ionic cell.
(c) assembling of lithium ion battery:
By positive plate, barrier film, negative plate in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward injecting electrolyte by the liquid injection port being arranged on battery container in battery container, sealing liquid injection port, obtains lithium ion battery.
Wherein, what the electrolyte of lithium ion battery was selected is the LiTFSI/ propene carbonate of 1mol/L, and barrier film adopts U.S. celgard 2400 polypropylene porous films.
Battery performance test:
Table 1, for the lithium ion battery that makes by the method in embodiment 5～8 is at 60 ℃ of temperature, carries out the result after charge-discharge test and 1000 circulations.
The data of the comparative example in table are to make capability retention after collector circulation 300 times (positive electrode and electrolyte are identical with corresponding embodiment's) with aluminium foil.Capability retention is higher, and lithium ion battery good cycling stability is described, concentration of electrolyte is 1mol/L.
Table 1
Figure BSA00000777615300091
Table 1 has been listed the lithium ion battery of test result: embodiment 5～8, anodal has all adopted the compound collector of aluminium foil/carbon of the present invention as preparing material, and lithium ion cell positive in comparative example has adopted aluminium foil of the prior art as preparing material.As can be seen from Table 1, after charge-discharge test and 1000 circulations, the capability retention of the lithium ion battery of embodiment 5～8 is respectively 97.1%, 88.5%, 93.4% and 95.2%, under same negative material and electrolyte, comparative example is made with aluminium foil the capability retention that collector only circulates after 300 times and is corresponded to respectively 84.5%, 78.9%, 81.1%, 84.2%, all lower than the capability retention of the lithium ion battery of embodiment 5～8 correspondences.The anodal lithium ion battery that has adopted aluminium foil/carbon composite current collector of the present invention of this explanation, good cycling stability, performance is far superior to using in prior art aluminium foil and as positive pole, prepares the lithium ion battery of material.
Reason is, the lithium ion battery that just very aluminium foil/carbon composite current collector of the present invention makes, embeds carbon-coating and aluminium foil by Implantation mutually, in conjunction with tight, realize the natural transition of carbon and aluminium, be conducive to reduce the contact internal resistance of the two, make the performance of aluminium carbon implanted layer be better than carbon coating.The compound implanted layer of aluminium foil/carbon produces rough surface after excessive erosion, can increase the compound bonding force with applying slurry of aluminium foil/carbon, the more coarse combination that is more conducive to the two in surface, because having the carbon of part after corrosion can come out, so the compound implanted layer of aluminium foil/carbon can directly contact coating slurry, also reduced the contact resistance of the two simultaneously, improved cyclical stability and the life-span of electrode, the capability retention after 1000 times that circulates can reach 97.1%.It is simple that while lithium ion battery of the present invention also possesses preparation technology, the advantage that cost is low.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, therefore protection scope of the present invention should be as the criterion with the desired protection range of claims.

Claims (9)

1. a preparation method for aluminium foil/carbon composite current collector, is characterized in that, comprises the steps:
(a) decontamination is dry: first by aluminium foil wipe oil dry;
(b) Implantation: by dried described aluminium foil, put into ion implantation device, pass into protective gas after sealing; utilize the method for high-speed ion injection, carbon is injected into the one side of described aluminium foil, obtain described aluminium foil/carbon composite current collector; wherein, Implantation amount is 1 * 10 -6～1 * 10 -4g/cm 2, injection length is 1～20 minute, Implantation Energy is 800～1500eV;
(c) corrosion is dry: after Implantation completes, take out described aluminium foil/carbon composite current collector, another side at described aluminium foil/carbon composite current collector is that nonionic injection face is smeared polymethyl methacrylate, after coating, described aluminium foil/carbon composite current collector is put into and in acid solution, carried out surface corrosion, after corrosion, use washed with de-ionized water erosional surface, until deionized water is neutral, then removes polymethyl methacrylate, and can use after described aluminium foil/carbon composite current collector is dry.
2. preparation method according to claim 1, is characterized in that, described acid solution is a kind of in hydrochloric acid, nitric acid, sulfuric acid, and the concentration of described acid solution is 0.01～1mol/L.
3. preparation method according to claim 1, it is characterized in that, in described step (a), be specially: with ethanol, acetone and deionized water, in described ultrasonic cleaning instrument, remove respectively the greasy dirt of described aluminium foil, and be dried 5～10 minutes in the vacuum drying chamber of 80～100 ℃.
4. preparation method according to claim 1, is characterized in that, in described step (b), described protective gas is a kind of in nitrogen, helium or argon gas.
5. preparation method according to claim 1, it is characterized in that, in described step (c), the time that the Implantation face of described aluminium foil/carbon composite current collector is corroded is 10～300 minutes, and described aluminium foil/carbon composite current collector is dried to 10～24 hours in the vacuum drying chamber of 60～80 ℃.
6. aluminium foil/carbon the composite current collector that adopts the arbitrary described preparation method of claim 1 to 5 to make.
7. a lithium ion battery, comprise by positive plate, barrier film, negative plate in order the stacked battery core forming, for installing the closed shell of described battery core, and filling is at the electrolyte of closed shell, described positive plate comprises collector and is coated in the positive electrode on this collector, it is characterized in that, described collector adopts aluminium foil/carbon composite current collector claimed in claim 6.
8. lithium ion battery according to claim 7, it is characterized in that, described positive electrode comprises the positive electrode active materials mixing at 85: 5: 10 in mass ratio, the acetylene black that plays the Kynoar of binding agent effect and play conductive agent effect, and described positive electrode active materials is LiFePO4, LiMn2O4 or cobalt acid lithium.
9. lithium ion battery according to claim 7, is characterized in that, the solute in described electrolyte is LiPF 6, LiBF 4, LiTFSI (LiN (SO 2cF 3) 2), LiFSI (LiN (SO 2f) 2) in a kind of; Solvent in described electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile; Described solute in described electrolyte and the volume ratio of described solvent are 1: 1, and the concentration of described electrolyte is 1mol/L.
CN201210339618.1A 2012-08-31 2012-08-31 Aluminium foil/carbon composite current collector, its preparation method and lithium ion battery Active CN103682366B (en)

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CN105870457A (en) * 2016-06-06 2016-08-17 南京航空航天大学 Aluminum foil current collator with surface modified and application thereof
WO2017190362A1 (en) * 2016-05-06 2017-11-09 深圳先进技术研究院 Negative electrode material, preparation method therefor, negative electrode and secondary battery comprising negative electrode material
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CN105304903A (en) * 2014-06-26 2016-02-03 Sk新技术株式会社 Secondary battery with improved high-temperature and low-temperature properties
CN105304903B (en) * 2014-06-26 2019-06-21 Sk新技术株式会社 Hot properties and the excellent secondary cell of low-temperature characteristics
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CN108565495A (en) * 2018-04-26 2018-09-21 北京石墨烯研究院 high-voltage lithium ion battery
CN114678533A (en) * 2022-04-07 2022-06-28 江苏卓高新材料科技有限公司 Positive electrode current collector and preparation method thereof, positive plate and preparation method thereof, and battery

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