CN107706356A - A kind of lithium ion battery silicon lattice structure electrode - Google Patents
A kind of lithium ion battery silicon lattice structure electrode Download PDFInfo
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- CN107706356A CN107706356A CN201710915194.1A CN201710915194A CN107706356A CN 107706356 A CN107706356 A CN 107706356A CN 201710915194 A CN201710915194 A CN 201710915194A CN 107706356 A CN107706356 A CN 107706356A
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- lattice structure
- silicon
- electrode
- lithium ion
- ion battery
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/70—Carriers or collectors characterised by shape or form
-
- 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 present invention discloses a kind of lithium ion battery silicon lattice structure electrode, and the electrode is different from traditional lithium ion cell electrode, is three-dimensional equally distributed lattice structure.Various sizes of electrode can be obtained by changing the accumulation number of plies, each layer number of arrays, the size of monomer structure of monomer structure, to meet different requirements.This silicon lattice electrode can accommodate volumetric expansion of the silicon in embedding lithium, reduce crackle and produce and extend, it is ensured that the service life of battery.The copper lattice structure as supporting frame and collector has higher yield strength simultaneously, can improve the mechanical stability of electrode material.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of lithium ion battery silicon lattice structure electrode.
Background technology
Lithium ion battery occupies leading position in the power supply market of wireless electronic product, and has in fields such as electric automobiles
More and more extensive application.Conduction and the reaction of active material and electrolyte by collector, battery electrode play it is conductive with
Form the effect of current loop.Battery electrode decides the size of battery capacity, and its cycle life also directly affects making for battery
Use the time.
Commercial li-ion battery capacity still has much room for improvement at present.Anode material used in conventional commercial lithium ion battery is generally
Graphite, its theoretical capacity are limited to 372mAh/g, it is impossible to meet the needs of to lithium battery Large Copacity.By contrast, the theory of silicon
The very a height of 4200mAh/g of capacity, decuples graphite.Silicon is used as the anode material of lithium ion battery, and battery capacity can be greatly improved,
Improve the situation of current battery off-capacity.
Silicon also can cause electrode while high power capacity is realized along with very big Volume Changes, being widely varied for volume
The Crack Extension of material, fracture, make battery capacity reduce rapidly, the lost of life, so as to limit silicon as lithium ion battery sun
The popularity of pole material.
The content of the invention
The technical problem that the present invention uses for：Volumetric expansion produces greatly during for silicon as lithium ion battery anode material
The problem of, there is provided a kind of lithium ion battery silicon lattice structure electrode and preparation method, using lattice structure, held using dot matrix hole
Receive volumetric expansion, and both ensured what silicon had as anode material as supporting frame and collector using copper lattice structure
Large Copacity enhances the mechanical robustness of electrode again.
The technical solution adopted by the present invention is：A kind of lithium ion battery silicon lattice structure electrode, the silicon lattice structure electricity
Extremely three-dimensional equally distributed silicon lattice structure, using copper to support structure inside the three-dimensional equally distributed silicon lattice structure
Frame and collector, adhere to one layer of silicon in the outer surface of copper, using monomer as basic component units, each monomer includes silicon lattice structure
Four vertical thick columns and four oblique buttress shafts, on the section vertical with vertical thick column axis, in four vertical thick columns
The line of the heart forms a square, and four root posts occupy square four summits, the column diagonal in square respectively
Respectively there is a connection of buttress shaft diagonal cross at both ends, each buttress shaft intersect at center a bit, by change monomer the accumulation number of plies,
The size of each layer number of arrays and lattice structure, i.e., by changing monomer number of permutations in the vertical and horizontal direction and each
The angle of the diameter of post, column and batter post, to obtain various sizes of electrode, to meet that the use of different size and shapes will
Ask.
The material of the lithium ion battery silicon lattice structure electrode is copper and silicon, and photoetching is also used in preparation process
Glue.
The silicon lattice structure electrode uses two-photon photoetching, plating and plasma enhancing successively in preparation process
Chemical gaseous phase depositing process.
The silicon lattice structure electrode is used for the lithium ion battery that anode material is silicon.
The silicon lattice structure electrode hole is uniform, can volumetric expansion of the accommodate electrod material silicon in embedding lithium.
Beneficial effect of the present invention compared with conventional graphite electrodes and common silicon electrode：
(1) compared with conventional graphite electrodes, silicon electrode structure of the invention is autonomous Design, its structure and existing graphite electricity
It is extremely different.This electrode has very high lithium capacity, and applied to lithium ion battery, battery capacity can be greatly improved, improve cell performance
Can, meet the needs of to battery Large Copacity.
(2) silicon lattice electrode of the invention can strengthen the yield strength of electrode using copper lattice structure as supporting frame.
(3) present invention using double-photon optical scribes Preparation Method, accurately controls the geometry of lattice electrode, characteristic size, hole
Gap, surface area, the desired design of designer can be realized ideally.
(4) compared with common silicon electrode, silicon lattice structure electrode interior hole of the present invention can accommodate exhausted big portion after the embedding lithium of silicon
Partial volume expands, and reduces crackle and produces and extend, can also ensure the service life of battery while improving capacity of lithium ion battery.
(5) hole is uniform everywhere for silicon lattice structure of the invention, and it is swollen can preferably to accommodate more uniform volume everywhere
It is swollen, so that institute is loaded consistent everywhere.
(6) using plasma strengthens chemical gaseous phase depositing process in silicon lattice structure electrode of the present invention, and siliceous deposits is existed
Copper surface, lithium diffusion length can be shortened, reduce differential expansion, improve mechanical stability.
(7) silicon lattice structure electrode of the present invention can be by changing the diameter of column, buttress shaft, and between column and oblique buttress shaft
The parameters such as angle adjust the physical dimension of electrode.
(8) present invention used in silicon be amorphous silicon, compared to crystalline silicon, amorphous silicon due to its micro-structural isotropism and
With more preferable mechanical performance, its electric property is also more excellent, can improve electrode performance.
Brief description of the drawings
Fig. 1 is the structure type of monomer in silicon lattice structure electrode in the present invention；
Fig. 2 is the schematic cross-section of the thick column of single vertical or oblique buttress shaft in the silicon lattice structure；
Fig. 3 is that the monomer of silicon lattice structure is extension signal in horizontal direction in the direction vertical with vertical pillars axis
Figure；
Fig. 4 be silicon lattice structure monomer along vertical pillars axis direction be extension schematic diagram on vertical direction；
Fig. 5 is the extension schematic diagram of the monomer of silicon lattice structure in the horizontal and vertical directions；
Fig. 6 is the monomer schematic diagram of silicon lattice structure after change structural parameters.
Embodiment
Below in conjunction with the accompanying drawings and example the present invention is described in detail.
Lithium ion cell electrode of the present invention is using two-photon photoetching, plating and plasma enhanced chemical vapor deposition etc.
Prepared by method, above-mentioned preparation method precision is high, and more ripe.And a kind of lattice structure is devised, it can be wanted according to using
Ask adjusting parameter, or the lattice structure of design other forms.Dot matrix has diversified structure, but due to each after the embedding lithium of silicon
Partial volume expansion is more uniform, therefore the hole in lattice structure should be also uniformly distributed, in consideration of it, in design as far as possible hole
Gap distribution arrangement is reasonable.
Designed lattice structure electrode is different from the traditional electrode mode of production, but remaining composition of battery is unaffected, because
This whole cell manufacturing process need to only change the preparation technology and battery packaging technology of electrode.
The specific embodiment of the present invention is as follows：
The present invention can be set out according to volumetric expansion by the Basic Design thinking that hole is accommodated, it is believed that electrode uses dot matrix knot
Structure is very suitable because the hole of lattice structure can receiving volume expansion, lattice structure can also strengthen the mechanical performance of electrode, from
And it can greatly improve battery performance.Copper, silicon etc. are by two-photon photoetching, plating and plasma enhanced chemical vapor deposition
The methods of silicon lattice electrode as shown in drawings is made.
It is below the adjustment explanation of designed silicon lattice electrode structural parameters：
As shown in figure 1, the monomer structure of the silicon lattice structure electrode of the present invention is：Vertical with vertical thick column axis
On section, the line at four vertical thick column centers forms a square, and vertical thick column l1, l2, l3, l4 are occupied just respectively
Respectively there is oblique buttress shaft l5, l6, l7, l8 interconnection at square four summits, the diagonal column both ends of square, and each oblique
Buttress shaft intersects at a bit of center.In Fig. 1 vertical thick column l1, l3 and oblique buttress shaft l5, l7 and vertical slightly column l2, l4 and
Angle is 45 degree between oblique buttress shaft l6, l8, and vertical thick a diameter of 2.5 microns of column l1, l2, l3, l4, length is 10 micro-
Rice, oblique a diameter of 1 micron of buttress shaft l5, l6, l7, l8.
As shown in Fig. 2 the structure of the thick column of single vertical or oblique buttress shaft is：As supporting frame and the copper of collector,
It is the inside constituent of vertical thick column and oblique buttress shaft；As the silicon of Anode of lithium cell main electrode material, copper is attached to
Outside.A diameter of 2 microns of vertical thick column internal copper, the thickness of outer silicone layer is 0.25 micron；Oblique buttress shaft internal copper
A diameter of 0.8 micron, the thickness of outer silicone layer is 0.1 micron.By calculating and testing, in silicon lattice structure electrode
In monomer, copper and silicon occupy about 30%, 17% monomer volume respectively, and the volume of residue about 53% is space in monomer, with
Accommodate the volumetric expansion that silicon can reach 300% in theory in charge and discharge process.
As shown in figure 3, the template as most original, monomer 1 can respectively on direction A, B shift copy to monomer 2
With monomer 3, so as to extend monomer structure, change electrode area in the horizontal plane and shape, so as to obtain designer institute
Intended effect.During foregoing shift copy, monomer 1 and monomer 2 share vertical thick column l2, l3, and monomer 1 and monomer 3 are common
With vertical thick column l1, l2, i.e., the vertical thick column of critical part is shared in horizontal direction between two adjacent monomers, and it is oblique
Buttress shaft is then present in inside each monomer.It is illustrated as the structure of horizontal direction 2 × 2.
As shown in figure 4, the template as most original, monomer 1 to monomer 5, can change electrode by shift copy in direction c
Thickness on vertical thick column axis direction, so as to be controlled to the thickness of electrode.During foregoing shift copy,
Vertical thick column l1, l2, l3, l4 in monomer 1 is extended, can obtain the vertical thick column of monomer 5, i.e., on vertical direction
Vertical thick column is coaxial between two adjacent monomers.
As shown in figure 5, the template as most original, monomer 1 can respectively on direction A, B, C shift copy to monomer 2,
3rd, 4,5,6,7 and 8, therefore the size of electrode can be designed in the horizontal and vertical directions, so as to needed for
Electrode volume and shape carry out flexible design.
As shown in fig. 6, based on monomer 1, by adjusting vertical thick column l1, l2, l3, l4 diameter and length, tiltedly
Diameter to buttress shaft l5, l6, l7, l8 and the vertical thick corner dimension between column and oblique buttress shaft being connected, can be right
The structure of monomer is designed and adjusted, and is finally reached expected design object.
It is specific preparation process below：
(1) according to electrode used therein volume and shape, by extension of the monomer structure in horizontally and vertically direction, in computer
Design corresponding lattice structure；Photoresist is placed on the glass substrate that applied thickness is 15nm gold, solidifies 3 points at 110 DEG C
Clock, geometric figure structure is portrayed on photoresist layer by exposed and developed, then by etching technics by the figure on photomask
Shape is transferred on institute's substrate, i.e. double-photon optical lithography, is directly carved into the lattice structure of computer design in the photoresist；
(2) using above-mentioned photoresist as three-dimensional template come electro-coppering, with Cu electrodes and Ag/AgCl reference electrodes
Constant current Cu electro-deposition is carried out in three electrode assemblies.Electroplating bath is by 100g/l CuSO4·5H2O, 200g/l H2SO4With commercial Cu
Electroplating additive forms, wherein commercial Cu electroplating additives composition includes 5ml/l 205M, 1ml/l 205KA and 1ml/
l205KR.This process deposits on photoresist surface that to adhere to good thickness be about 1 micron one thin using electrolysis principle
Layer copper；
(3) photoresist by electro-coppering obtained above is placed in 1-Methyl-2-Pyrrolidone, removes remaining photoetching
After glue, copper lattice structure is obtained, passes through plasma enhanced chemical vapor deposition method, at 200 DEG C, gas before 5% silane
One layer of amorphous silicon is deposited on foregoing copper lattice structure and substrate with 250sccm flow velocity and 800mTorr pressure, held
It is continuous 30 minutes, it can be sunk in the amorphous silicon coating that deposit thickness is about 0.25 micron in copper lattice structure and in flat substrate
The amorphous silicon that product thickness is about 0.75 micron.
Prepare after completing, dependence test is carried out to the silicon lattice electrode of the present invention.
In embedding lithium for the first time/de- lithium circulation, observed using SEM, copper table is attached in silicon lattice structure
The volumetric expansion in process of intercalation of the silicon in face reaches 200% or so, can be sufficient filling with space, and silicon lattice structure has no obvious
Crackle, and observe that silicon grain is i.e. cracked during first time is circulated before, so designed silicon lattice structure has
Accommodate the more uniform expansion of silicon, slow down the advantages of crackle generation or extension, so as to extend electrode life, increase battery and use
Time.
The copper lattice structure for not electroplating silicon is prepared, its yield strength is measured up to 300MPa, far above the surrender of fine copper
Intensity.It is compressed along vertical thick column axis direction, silicon lattice electrode shows mechanicalness that will be excellent than copper, silicon
Can, therefore use copper lattice structure can improve the resistance to compression survivability of electrode as supporting frame.
It is polycrystal that copper in electrode, which can be observed, using transmission electron microscope, and silicon is amorphous state.The poplar of amorphous silicon
Family name's modulus is 71GPa~550GPa, and the Young's modulus of crystalline silicon is 140~150GPa, and except mechanical performance, amorphous silicon is led
Electrical property is also more excellent than crystalline silicon, and this can improve the mechanical strength and electric property of silicon lattice structure electrode.
In previous designs and the silicon lattice structure electrode prepared, vertical thick column, oblique buttress shaft and thick column with it is thin
Angle between post has only selected one group, and during practical operation, above-mentioned parameter can be suitably adjusted when monomer structure is designed in computer,
To reach expected design effect.
Above example is provided just for the sake of the description purpose of the present invention, rather than limitation the scope of the present invention.The present invention
Scope be defined by the following claims.The various equivalent alterations and modifications for not departing from spirit and principles of the present invention and making,
It all should cover within the scope of the present invention.
Claims (5)
- A kind of 1. lithium ion battery silicon lattice structure electrode, it is characterised in that：The silicon lattice structure electrode is uniform for three-dimensional The silicon lattice structure of distribution, using copper as supporting frame and collector inside the three-dimensional equally distributed silicon lattice structure, One layer of silicon is adhered in the outer surface of copper, and using monomer as basic component units, each monomer includes four and vertically slightly stood silicon lattice structure Post and four oblique buttress shafts, on the section vertical with vertical thick column axis, the line composition at four vertical thick column centers One square, and four root posts occupy square four summits respectively, the column both ends diagonal in square respectively have one Buttress shaft diagonal cross connects, each buttress shaft intersect at center a bit, by change the accumulation number of plies of monomer, each layer number of arrays with And the size of lattice structure, i.e. the diameter, vertical by changing monomer number of permutations in the vertical and horizontal direction and each post The angle of post and batter post, to obtain various sizes of electrode, to meet the requirement to different size and shape electrodes.
- A kind of 2. lithium ion battery silicon lattice structure electrode according to claim 1, it is characterised in that：The lithium ion battery silicon The material of lattice structure electrode is copper and silicon, and photoresist is also used in preparation process.
- 3. according to a kind of lithium ion battery silicon lattice structure electrode of claim 1 or 2, it is characterised in that：The silicon dot matrix knot Structure electrode uses two-photon photoetching, plating and plasma enhanced chemical vapor deposition method successively in preparation process.
- A kind of 4. lithium ion battery silicon lattice structure electrode according to claim 1, it is characterised in that：The silicon lattice structure electricity Pole is used for the lithium ion battery that anode material is silicon.
- A kind of 5. lithium ion battery silicon lattice structure electrode according to claim 1, it is characterised in that：The silicon lattice structure electricity Pole hole is uniform, can volumetric expansion of the accommodate electrod material silicon in embedding lithium.
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| CN201710915194.1A CN107706356A (en) | 2017-09-29 | 2017-09-29 | A kind of lithium ion battery silicon lattice structure electrode |
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| CN201710915194.1A CN107706356A (en) | 2017-09-29 | 2017-09-29 | A kind of lithium ion battery silicon lattice structure electrode |
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| CN107706356A true CN107706356A (en) | 2018-02-16 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683656A (en) * | 2012-04-26 | 2012-09-19 | 宁波杉杉新材料科技有限公司 | High-performance porous film silicon-based negative electrode material of lithium ion cell and preparation method thereof |
| CN103213933A (en) * | 2013-03-27 | 2013-07-24 | 厦门大学 | Nano electrode structure for silicon-based three-dimensional micro-battery |
-
2017
- 2017-09-29 CN CN201710915194.1A patent/CN107706356A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683656A (en) * | 2012-04-26 | 2012-09-19 | 宁波杉杉新材料科技有限公司 | High-performance porous film silicon-based negative electrode material of lithium ion cell and preparation method thereof |
| CN103213933A (en) * | 2013-03-27 | 2013-07-24 | 厦门大学 | Nano electrode structure for silicon-based three-dimensional micro-battery |
Non-Patent Citations (2)
| Title |
|---|
| JENS BAUER等: ""Nanolattices: An Emerging Class of Mechanical Metamaterials"", 《ADV. MATER.》 * |
| XIAOXING XIA等: ""In Situ Lithiation−Delithiation of Mechanically Robust Cu−Si Core−Shell Nanolattices in a Scanning Electron Microscope"", 《ACS ENERGY LETT.》 * |
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Application publication date: 20180216 |