CN106684387A - Lithium ion battery negative electrode comprising diamond-like thin film layer, preparation method for negative electrode, and lithium ion battery - Google Patents
Lithium ion battery negative electrode comprising diamond-like thin film layer, preparation method for negative electrode, and lithium ion battery Download PDFInfo
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- CN106684387A CN106684387A CN201611185452.7A CN201611185452A CN106684387A CN 106684387 A CN106684387 A CN 106684387A CN 201611185452 A CN201611185452 A CN 201611185452A CN 106684387 A CN106684387 A CN 106684387A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
Abstract
The invention provides a lithium ion battery negative electrode comprising a diamond-like thin film layer. The negative electrode comprises a conductive current collector, a negative electrode active material layer arranged on the conductive current collector and a diamond-like thin film layer deposited on the surface of the negative electrode active material layer; and the diamond-like thin film layer comprises doped elements, wherein the doped elements comprises one or more of Si, B, N, P, Al, Be, Mg, Ti, Cr, W, Fe, Zr, Pt, Mo, Co, Ni and Sb. According to the lithium ion battery negative electrode, the diamond-like thin film layer is deposited on the surface of the negative electrode active material layer, and the diamond-like thin film layer has excellent electrochemical inertness and conductivity and high mechanical strength, so that occurrence of an unstable SEI layer on the surface of the negative electrode active material is avoided, and the cycling stability of the electrode is greatly improved. The invention also provides a preparation method for the lithium ion battery negative electrode, and the lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of lithium ion battery negative and preparation method thereof
And lithium ion battery.
Background technology
The exploitation of high-performance electrode is the key that performance of lithium ion battery is lifted, and is also the focus and difficult point of current research.
Negative material plays a crucial role in the performance of lithium battery, particularly in capacity and in terms of the life-span.Silicon, germanium, stannum, oxo transition metal
The novel anode materials such as compound, metal nitride all show higher capacity of negative plates and good chemical property.But this
The not good problem of a little material generally existing stability, seriously constrains its industrialization process.And in actual battery application, with
The increase of cycle-index, the SEI films of electrode surface can be destroyed because of constantly expanding, shrinking, and constantly expose new
Electrode active material reacts with electrolyte, new SEI layers is generated, so as to the chemical property for causing electrode fails.Therefore,
It is to improve the key of novel anode material performance to reduce and eliminate the unnecessary interfacial reaction in negative material surface.
At present, widespread practice is to wrap up one layer of several nanometers of carbon to tens nanometer thickness on these novel anode material surfaces
Layer is combined negative material and grapheme material.But these materials cannot still keep non-during charge and discharge cycles
Often stable structure, it is limited to improving the help of cyclical stability of negative pole, because above-mentioned carbon-coating is with sp2 phases with amorphous carbon
It is main, diamond phase is practically free of, its poor mechanical property, chemical stability is not also high, always shows low electrical conductivity, substantial amounts of
Dangling bonds can also cause chemistry and the electrochemical reaction between electrolyte.Therefore there is higher physics and chemical stability, can
Have to be developed with the negative material protective layer for forming stable SEI layers.
The content of the invention
In consideration of it, first aspect present invention provide a kind of lithium ion battery negative containing diamond like carbon film layer, its
Anode active material layer surface deposition has diamond like carbon film layer, because diamond like carbon film layer has excellent electrochemicaUy inert
With electric conductivity, high mechanical strength, thus the appearance of the unstable SEI layers in negative active core-shell material surface is avoided, be greatly improved
The cyclical stability of electrode.
Specifically, in a first aspect, the invention provides a kind of lithium ion battery negative containing diamond like carbon film layer, including
Conductive current collector, the anode active material layer being arranged in the conductive current collector and it is deposited on the negative active core-shell material
The diamond like carbon film layer of layer surface, in the diamond like carbon film layer include doped chemical, the doped chemical include Si, B,
One or more in N, P, Al, Be, Mg, Ti, Cr, W, Fe, Zr, Pt, Mo, Co, Ni and Sb.
Diamond like carbon film layer has high mechanical strength and excellent electrochemicaUy inert, can be with holding electrode overall structure
Stability, effectively prevent the electrode material electrode overall volume that internal huge change in volume is caused in charge and discharge process
Change.Simultaneously such diamond film layer has high electronics, Particle Delivery efficiency, does not interfere with the performance of electrode.Diamond-like
Stone thin layer is also possible to play prevents Li dendrite from piercing through barrier film, improving the effect such as inside battery thermal diffusion.And it is thin to diamond like carbon
Film layer carries out doping in situ, diamond like carbon film layer can be caused to have less interface resistance and higher electrical conductivity, more favorably
In the transmission of electronics.
The carbon content of the sp3 hydridization in the diamond like carbon film layer is higher, film layer mechanical property and chemically stable
Property it is all higher, but electric conductivity is necessarily affected, sp2 phases are that graphite-phase can improve electric conductivity, but affect diamond like carbon
The protective value of thin layer, therefore in order to obtain diamond like carbon film layer of good performance, the ratio of sp3 and sp2 can be entered
Row regulation and control.
In the present invention, the diamond like carbon film layer can for tetrahedral amorphous carbon (ta-C) film, amorphous carbon (a-C) film, four
Face body contains hydrogen amorphous (ta-C:H) film or containing hydrogen amorphous (a-C:H) film.Amorphous carbon (a-C) film is former by sp3 and sp2 keys carbon
The three-dimensional network that mutually mixes of son is constituted, and it by the sp3 keys carbon atom more than 80% is skeleton that tetrahedral amorphous carbon (ta-C) film is
Constitute.
Alternatively, the thickness of the diamond like carbon film layer is 10nm-1 μm.Still optionally further, the diamond like carbon is thin
The thickness of film layer is 50nm-800nm, 100nm-500nm.Suitable thicknesses of layers not only can allow lithium ion by and expand
Dissipate, keep higher ion transmission efficiency, while the formation of unstable SEI layers can also be prevented effectively, improve electrode cycle and stablize
Property.
In the diamond like carbon film layer, the addition of doped chemical can improve the electric conductivity of diamond like carbon film layer, make
Thin film realizes the conductive even metallic conduction of semimetal.Depending on concrete doping is according to different doped chemicals.By taking boron element as an example,
In the diamond like carbon film layer, the content of boron element is 1019-1021Atom/cm3。
Alternatively, the diamond like carbon film layer can be heavy using electron cyclotron resonace assisted microwave synthesis plasma enhanced chemical vapor
Product (ECR-MWPCVD), hot-wire chemical gas-phase deposition (HFCVD), magnetron sputtering, ion beam assisted depositing, pulsed laser deposition or
The mode of vacuum cathode arc deposition is prepared in the anode active material layer.
The anode active material layer includes negative active core-shell material, and the anode active material layer includes negative electrode active material
Material, the negative active core-shell material can be silica-base material (such as silicon nanowires, nano-tube and silica flour), graphite, germanium, stannum, mistake
Cross metal-oxide (the such as binary oxide and ternary oxide of Co, Fe, Mo, Ni, V, Ti, Zn metal) and metal nitride
In one or more.The anode active material layer may also include conductive agent and binding agent, conductive agent be white carbon black, acetylene black,
Delanium, native graphite etc., binding agent is carboxymethyl cellulose, Kynoar, politef, polyvinyl alcohol, polyamides
Imines etc., the anode active material layer thickness is about 0.5-200mm.
The conductive current collector is metal forming, such as metal copper foil or aluminium foil, and thickness is 10-100mm.
The lithium ion battery negative containing diamond like carbon film layer that first aspect present invention is provided, by negative electrode active material
Bed of material surface deposits the diamond like carbon film layer containing doped chemical, and such diamond film layer has excellent electrochemicaUy inert
With electric conductivity, high mechanical strength, it is to avoid the directly contact of negative active core-shell material and electrolyte, negative active core-shell material is reduced
With the side reaction of electrolyte, the formation of unstable SEI layers is effectively prevented, the cyclical stability of electrode greatly improved.
Second aspect, the invention provides a kind of preparation method of the lithium ion battery negative containing diamond like carbon film layer,
Comprise the following steps：
Conductive current collector is provided；
The coating in the conductive current collector prepares anode active material layer；
Deposition prepares diamond like carbon film layer in the anode active material layer, obtains the lithium containing diamond like carbon film layer
Ion battery negative pole；In the diamond like carbon film layer include doped chemical, the doped chemical include Si, B, N, P, Al, Be,
One or more in Mg, Ti, Cr, W, Fe, Zr, Pt, Mo, Co, Ni and Sb.
The mode that the deposition in anode active material layer prepares diamond like carbon film layer includes that electron cyclotron resonace is auxiliary
Help microwave plasma CVD (ECR-MWPCVD), hot-wire chemical gas-phase deposition (HFCVD), magnetron sputtering, ion
One kind in beam assistant depositing, pulsed laser deposition and vacuum cathode arc deposition.
Specifically, adopting ECR-MPCVD mode depositions to prepare the concrete operations of boron doped diamond thin layer can be for：
Methane is passed through in deposition process as carbon source, used as impurity gas, the doping ratio of B/C is 1000- to trimethyl borine (TMB)
10000ppm, microwave power is 100-1000W, and microwave plasma body frequency is 2.45GHz, and electromagnetic field intensity is 875 Gausses, is sunk
The base vacuum of product cavity is~10-7Torr, 25 DEG C of underlayer temperature holding, sedimentation time 1-10 hours, deposit thickness 10nm-1 μ
m。
Adopting ECR-MPCVD mode depositions to prepare the concrete operations of N doping diamond like carbon film layer can be for：Deposited
Methane is passed through in journey as carbon source, nitrogen is used as impurity gas, N2/CH4/H2N in gaseous mixture2Ratio be 10%-50%, CH4
Ratio be 2%-5%, microwave power is 100-1000W, and microwave plasma body frequency is 2.45GHz, and electromagnetic field intensity is 875
Gauss, the base vacuum of deposition chamber is~10-7Torr, 25 DEG C of underlayer temperature holding, sedimentation time 1-10 hours, deposit thickness
10nm-1μm。
Adopt magnetically controlled DC sputtering mode deposit prepare the concrete operations of boron doped diamond like carbon film layer can be for：It is heavy
Argon is passed through in vacuum chamber during product and composition target is opened, composition target is to be inlaid with boron particles in carbon target, and boron particles are by pure
Degree>95% amorphous boron powder is made.Adulterate boron in by adjusting boron particles and accounting for the ratio of carbon target area to control diamond like carbon
Content.It is 0.5-1.0Pa to adjust mass flowmenter and make the pressure in vacuum room, and target power output is 1-5KW, substrate bias 50-
200V, sedimentation time is 30-300min, 10nm-1 μm of deposit thickness.
Adopting ion beam assisted depositing mode deposition to prepare the concrete operations of boron doped diamond thin layer can be for：It is heavy
It is passed through in vacuum chamber acetylene during product, sputtering target is boron target, the pressure in vacuum room is 0.5-1.0Pa, ion source voltage
For 50-100V, substrate bias 50-200V, sedimentation time is 30-300min, 10nm-1 μm of deposit thickness.
The present invention carries out the preparation of diamond like carbon film layer using said method, will not to anode active material layer structure and
Composition is damaged, low temperature depositing, more uniform, is readily available thin layer, continuous fine and close diamond like carbon film.
The preparation method of the lithium ion battery negative containing diamond like carbon film layer that second aspect present invention is provided, technique letter
It is single, beneficial to large-scale production.
The third aspect, the present invention has also supplied a kind of lithium ion battery, including positive pole, negative pole, electrolyte, barrier film, described negative
The lithium ion battery negative containing diamond like carbon film layer that extremely first aspect present invention is provided.
The lithium ion battery that third aspect present invention is provided, with good cyclical stability.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to description
, or can be known by the enforcement of the embodiment of the present invention.
Description of the drawings
Fig. 1 is the structural representation of the lithium ion battery negative containing diamond like carbon film layer prepared by the embodiment of the present invention 1；
Fig. 2 is that the diamond like carbon of the lithium ion battery negative containing diamond like carbon film layer prepared by the embodiment of the present invention 1 is thin
The Raman spectrogram of film layer；
Fig. 3 is the lithium ion and electric transmission schematic diagram of lithium ion battery prepared by the embodiment of the present invention 1；
Fig. 4 is that lithium ion battery prepared by the embodiment of the present invention 1 is tested with the cycle performance of the lithium ion battery of comparative example 1
Comparison diagram.
Specific embodiment
Described below is the preferred implementation of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of without departing from embodiment of the present invention principle, some improvements and modifications can also be made, these improvement
With the protection domain that retouching is also considered as the embodiment of the present invention.
Multiple embodiments are divided to be further detailed the embodiment of the present invention below.Wherein, the embodiment of the present invention is not limited
Due to following specific embodiment.In the range of constant principal right, can be appropriate carry out change enforcement.
Embodiment 1
A kind of preparation method of the lithium ion battery negative containing diamond like carbon film layer, comprises the following steps：
(1) a piece of monocrystalline silicon piece is taken, resistivity is less than 5m Ω ﹒ cm, silver nitrate and hydrogen is added in polytetrafluoroethylcontainer container
The mixed aqueous solution (wherein, silver nitrate concentration is 0.005M and hydrofluoric acid concentration is 4.8M) of fluoric acid, by silicon chip the solution is immersed
In 1 minute, (hydrofluoric acid concentration is 4.8M and hydrogen peroxide then silicon chip extracting to be placed on into the mixed solution of Fluohydric acid. and hydrogen peroxide
Concentration is 0.3M) in kept for 30 minutes, silicon chip is rinsed with water after taking-up, and is immersed in (1 in the salpeter solution of dilute with water:1v/
V) silver catalyst, subsequent 60 DEG C of drying are removed.Silicon nanowires is separated with monocrystalline silicon piece substrate, as negative active core-shell material.
(2) by silicon nanowires：Acetylene black：Carboxymethyl cellulose (CMC) mass ratio is 8:1:1 ratio is uniform by three
In being dispersed in N-Methyl pyrrolidone (NMP), finely dispersed slurry is uniformly mixed and made in mortar, gained slurry is uniform
It is coated on the metal copper foil of cleaning, is then placed in 80 DEG C of vacuum drying oven and is dried 24 hours, takes out afterwards coated
Copper Foil is pressed into disk Jing after Kun press Kun pressures with the tablet machine of 12mm, obtains the Copper Foil with anode active material layer；
(3) boron doped p type conduction is prepared in the surface deposition of the anode active material layer using ECR-MPCVD modes
Diamond like carbon film layer, is passed through methane as carbon source in deposition process, used as impurity gas, B/C's mixes trimethyl borine (TMB)
Miscellaneous ratio is 1000-10000ppm, and microwave power is 100-1000W, and microwave plasma body frequency is 2.45GHz, electromagnetic field intensity
Spend for 875 Gausses, the base vacuum of deposition chamber is~10-7Torr, 25 DEG C of underlayer temperature holding, sedimentation time 1-10 hours,
10nm-1 μm of deposit thickness, deposition obtain ta-C diamond like carbon film layers, that is, prepare the lithium containing diamond like carbon film layer from
Sub- battery cathode.
Fig. 1 is the structural representation of the lithium ion battery negative containing diamond like carbon film layer prepared by the embodiment of the present invention 1；
In figure, 10 is conductive current collector, and 20 is anode active material layer, and 30 is diamond like carbon film layer.Fig. 2 is the embodiment of the present invention 1
The Raman spectrogram of the diamond like carbon film layer of the lithium ion battery negative containing diamond like carbon film layer for preparing.Can be with from Fig. 2
Find out, the Raman spectrum of diamond like carbon film shows one in 1200-1800cm-1In the range of asymmetric broad peak, wherein
Heart position is in 1500-1570cm-1Left and right, without the Raman peaks that the doping of obvious boron causes.
The preparation of lithium ion battery
The lithium ion battery negative with diamond like carbon film layer that the present embodiment is prepared as negative pole, with metal
Lithium piece as to electrode, with LiPF6Concentration is 1.0M, ethylene carbonate/diethyl carbonate/Ethyl methyl carbonate (EC/DMC/EMC)
Volume ratio is 1:1:The mixed solution of 1v/v/v is electrolyte, using microporous polypropylene membrane as barrier film, in the handss full of argon
Battery is assembled in casing.Fig. 3 is the lithium ion and electric transmission schematic diagram of lithium ion battery prepared by the embodiment of the present invention 1.
Comparative example
The Copper Foil with anode active material layer that the step of the embodiment of the present invention 1 (2) is prepared as negative pole, with gold
Belong to lithium piece as to electrode, with LiPF6Concentration is 1.0M, ethylene carbonate/diethyl carbonate/Ethyl methyl carbonate (EC/DMC/
EMC) volume ratio is 1:1:The mixed solution of 1v/v/v is electrolyte, using microporous polypropylene membrane as barrier film, full of argon
Glove box in be assembled into battery.
The conductive class of boron doped p type is prepared in the surface deposition of the anode active material layer using ECR-MPCVD modes
Diamond film layer, is passed through methane as carbon source in deposition process, trimethyl borine (TMB) is used as impurity gas, the doping of B/C
Ratio is 1000-10000ppm, and microwave power is 100-1000W, and microwave plasma body frequency is 2.45GHz, electromagnetic field intensity
For 875 Gausses, the base vacuum of deposition chamber is~10-7Torr, underlayer temperature is kept for 25 DEG C, and sedimentation time 1-10 hours are sunk
10nm-1 μm of thickness of product, deposition obtains ta-C diamond like carbon film layers, that is, prepares lithium ion battery negative.
After the battery standing a few hours that embodiment 1 and comparative example are assembled into, battery is entered using blue electricity cell tester
Row constant current charge-discharge test, electric current density is 100mAg-1, voltage range is 0.01-3.1V.Test result is as shown in Figure 4.From figure
4 as can be seen that the embodiment of the present invention deposited the silicon nanowires negative pole of diamond like carbon film layer, first discharge capacity and charging is held
Amount is respectively 4361.3mAg-1And 3084.9mAg-1, corresponding first charge-discharge coulombic efficiency is 70.73%.In 50 circle circulations
After, discharge capacity is maintained at 2599.3mA h g-1, it is 60% with respect to first circulation volume conservation rate.And in comparative example
The initial charge capacity of silicon nanowires negative pole is 1594.6mA h g-1, and initial charge capacity is 1343.8mA h g-1, first
Coulombic efficiency is 84.27%.Show higher initial coulomb efficiency, it is seen that the addition of diamond like carbon film layer needs to form volume
Outer SEI layers, there is certain impact on initial coulomb efficiency.However, comparative example is not provided with following for the negative pole of diamond like carbon film layer
Ring stability extreme difference, discharge capacity only 636.8mA h g after 25 circulations-1, discharge capacity only 180.5mA h after 50 circulations
g-1, with respect to first circulation volume conservation rate only 11%.
Embodiment 2
A kind of preparation method of the lithium ion battery negative containing diamond like carbon film layer, comprises the following steps：
(1) by silica flour：Acetylene black：Carboxymethyl cellulose (CMC) mass ratio is 8:1:1 ratio, three is dispersed
In N-Methyl pyrrolidone (NMP), finely dispersed slurry is uniformly mixed and made in mortar, gained slurry is uniformly coated
On clean metal copper foil, then it is placed in 80 DEG C of vacuum drying oven and is dried 24 hours, coated Copper Foil is taken out afterwards
Jing after Kun press Kun pressures, disk is pressed into the tablet machine of 12mm, obtains the Copper Foil with anode active material layer；
(2) it is conductive in the N-shaped that the surface deposition of the anode active material layer prepares N doping using ECR-MPCVD modes
Diamond like carbon film layer, methane is passed through in deposition process as carbon source, nitrogen is used as impurity gas, N2/CH4/H2In gaseous mixture
N2Ratio be 10%-50%, CH4Ratio be 2%-5%, microwave power is 100-1000W, and microwave plasma body frequency is
2.45GHz, electromagnetic field intensity is 875 Gausses, and the base vacuum of deposition chamber is~10-7Torr, underlayer temperature is kept for 25 DEG C, is sunk
Product time 1-10 hour, 10nm-1 μm of deposit thickness, deposition obtains ta-C or a-C diamond like carbon film, that is, prepares containing class
The lithium ion battery negative of diamond film layer.Wherein, depositing temperature is higher, and sp3 contents are higher, and control methane ratio is relatively low,
Doped chemical improves sp3 contents compared with I haven't seen you for ages, obtains ta-C films.
Embodiment 3
A kind of preparation method of the lithium ion battery negative containing diamond like carbon film layer, comprises the following steps：
(1) by tin base cathode material：Acetylene black：Carboxymethyl cellulose (CMC) mass ratio is 8:1:1 ratio, by three
In being dispersed in NMP, and finely dispersed slurry is uniformly mixed and made in mortar, gained slurry is coated uniformly on into cleaning
Metal copper foil on, be then placed in 80 DEG C of vacuum drying oven and be dried 24 hours, coated Copper Foil Jing Kun pressures are taken out afterwards
After machine Kun pressures, disk is pressed into the tablet machine of 12mm, obtains the Copper Foil with anode active material layer；
(2) the surface deposition using magnetically controlled DC sputtering in the anode active material layer prepares boron doped diamond like carbon
Thin layer, deposition process is：Argon is passed through in vacuum chamber and composition target is opened, composition target is to be inlaid with boron particles in carbon target,
Boron particles are by purity>95% amorphous boron powder is made.By adjusting boron particles the ratio of carbon target area is accounted for controlling diamond-like
The content of doping boron in stone.It is 0.5-1.0Pa to adjust mass flowmenter and make pressure in vacuum room, and target power output is 1-5KW, substrate
Bias 50-200V, sedimentation time is 30-300min, 10nm-1 μm of deposit thickness, and it is thin that deposition obtains N doping ta-C diamond like carbon
Film, that is, prepare the lithium ion battery negative containing diamond like carbon film layer.
Embodiment 4
A kind of preparation method of the lithium ion battery negative containing diamond like carbon film layer, comprises the following steps：
(1) by germanio negative material：Acetylene black：Carboxymethyl cellulose (CMC) mass ratio is 8:1:1 ratio, by three
In being dispersed in NMP, and finely dispersed slurry is uniformly mixed and made in mortar, gained slurry is coated uniformly on into cleaning
Metal copper foil on, be then placed in 80 DEG C of vacuum drying oven and be dried 24 hours, coated Copper Foil Jing Kun pressures are taken out afterwards
After machine Kun pressures, disk is pressed into the tablet machine of 12mm, obtains the Copper Foil with anode active material layer；
(2) boron doping eka-gold is prepared in the surface deposition of the anode active material layer using ion beam assisted depositing method
Diamond thin film layer.Deposition process is：Acetylene is passed through in vacuum chamber, sputtering target is boron target, and the pressure in vacuum room is 0.5-
1.0Pa, ion source voltage is 50-100V, and substrate bias 50-200V, sedimentation time is 30-300min, deposit thickness 10nm-1 μ
M, deposition obtains boron doping ta-C diamond like carbon film, that is, prepare the lithium ion battery negative containing diamond like carbon film layer.
Embodiment 5
A kind of preparation method of the lithium ion battery negative containing diamond like carbon film layer, comprises the following steps：
(1) by silica flour：Acetylene black：Carboxymethyl cellulose (CMC) mass ratio is 8:1:1 ratio, three is dispersed
In N-Methyl pyrrolidone (NMP), finely dispersed slurry is uniformly mixed and made in mortar, gained slurry is uniformly coated
On clean metal copper foil, then it is placed in 80 DEG C of vacuum drying oven and is dried 24 hours, coated Copper Foil is taken out afterwards
Jing after Kun press Kun pressures, disk is pressed into the tablet machine of 12mm, obtains the Copper Foil with anode active material layer；
(2) it is conductive in the N-shaped that the surface deposition of the anode active material layer prepares phosphorus doping using ECR-MPCVD modes
Diamond like carbon film layer, methane is passed through in deposition process as carbon source, phosphine gas is used as impurity gas, PH3/CH4/H2/Ar
PH in gaseous mixture3Ratio be 0.005%-0.5%, CH4Ratio be 1%-5%, H2Ratio be 1%-5%, remaining is Ar
Gas, microwave power is 100-1000W, and microwave plasma body frequency is 2.45GHz, and electromagnetic field intensity is 875 Gausses, deposition chamber
Base vacuum be~10-7Torr, 200 DEG C of underlayer temperature holding, sedimentation time 10min-1 hours, 10nm-1 μm of deposit thickness,
Deposition obtains ta-C diamond like carbon film, that is, prepare lithium ion battery negative.
It should be noted that according to the above description the announcement of book and and illustrate, those skilled in the art in the invention are also
Above-mentioned embodiment can be changed and changed.Therefore, the invention is not limited in concrete reality disclosed and described above
Mode is applied, some equivalent modifications and change to the present invention should also be as within the scope of the claims of the present invention.This
Outward, although some specific terms used in this specification, these terms merely for convenience of description, not to the present invention
Constitute any restriction.
Claims (10)
1. a kind of lithium ion battery negative containing diamond like carbon film layer, it is characterised in that including conductive current collector, be arranged on institute
State the anode active material layer in conductive current collector and be deposited on the diamond like carbon film on the anode active material layer surface
Layer, in the diamond like carbon film layer include doped chemical, the doped chemical include Si, B, N, P, Al, Be, Mg, Ti, Cr,
One or more in W, Fe, Zr, Pt, Mo, Co, Ni and Sb.
2. lithium ion battery negative as claimed in claim 1, it is characterised in that the diamond like carbon film layer includes tetrahedron
The hydrogeneous amorphous carbon-film of amorphous carbon-film, amorphous carbon-film, tetrahedron, hydrogeneous amorphous carbon-film.
3. lithium ion battery negative as claimed in claim 1, it is characterised in that the thickness of the diamond like carbon film layer is
10nm-1μm。
4. lithium ion battery negative as claimed in claim 1, it is characterised in that the diamond like carbon film layer is returned using electronics
Rotation resonance assisted microwave synthesis plasma activated chemical vapour deposition, hot-wire chemical gas-phase deposition, magnetron sputtering, ion beam assisted depositing,
The mode of pulsed laser deposition or vacuum cathode arc deposition is prepared in the anode active material layer.
5. lithium ion battery negative as claimed in claim 1, it is characterised in that the anode active material layer includes that negative pole is lived
Property material, the negative active core-shell material include silica-base material, graphite, germanium, stannum, transition metal oxide and metal nitride in
One or more.
6. lithium ion battery negative as claimed in claim 1, it is characterised in that the anode active material layer thickness is 0.5-
200mm。
7. lithium ion battery negative as claimed in claim 1, it is characterised in that the conductive current collector is metal copper foil or aluminum
Paper tinsel.
8. a kind of preparation method of the lithium ion battery negative containing diamond like carbon film layer, it is characterised in that comprise the following steps：
Conductive current collector is provided；
The coating in the conductive current collector prepares anode active material layer；
Deposition prepares diamond like carbon film layer in the anode active material layer, obtains the lithium ion containing diamond like carbon film layer
Battery cathode；In the diamond like carbon film layer include doped chemical, the doped chemical include Si, B, N, P, Al, Be, Mg,
One or more in Ti, Cr, W, Fe, Zr, Pt, Mo, Co, Ni and Sb.
9. the preparation method of lithium ion battery negative as claimed in claim 8, it is characterised in that described in negative active core-shell material
On layer deposition prepare diamond like carbon film layer mode include electron cyclotron resonace assisted microwave synthesis plasma activated chemical vapour deposition,
In hot-wire chemical gas-phase deposition, magnetron sputtering, ion beam assisted depositing, pulsed laser deposition and vacuum cathode arc deposition one
Kind.
10. a kind of lithium ion battery, it is characterised in that including positive pole, negative pole, electrolyte, barrier film, the negative pole is claim
The lithium ion battery negative containing diamond like carbon film layer described in any one of 1-7.
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