CN109932406A - A kind of electrode structure of in-situ observation lithium ion diffusion process - Google Patents
A kind of electrode structure of in-situ observation lithium ion diffusion process Download PDFInfo
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Abstract
The present invention relates to a kind of electrode structures of lithium ion diffusion way in in-situ observation graphite material.Be using circular working electrode structure, annular to electrode structure, constitute two electrodes by edge-to-edge's structure type of concentric circles position distribution in face；The diffusion mode of lithium ion is along electrode radial manner in electrode.Its working electrode shape is circle, is annular to electrode shape, and the internal diameter of annular electrode is greater than the outer diameter of circular electrode；Electric installation uses the copper metal pin with flange, and top is pressed on electrode material, and lower part is attached with conductive copper, realizes the connection of electrode material and outer lead.The present invention can carry out direct in-situ observation to the diffusion process of working electrode lithium ion in Li insertion extraction cyclic process, overcome immeasurable difficulty caused by the face-to-face mode of traditional electrode, the design of circular electrode simultaneously more meets the structure design of business electrode, can also realize that the diffusion in research all directions is developed.
Description
Technical field
The invention belongs to electrochemical fields, and in particular to the electricity of lithium ion diffusion way in a kind of in-situ observation graphite material
Pole structure.
Background technique
With the development of the new energy technologies such as lithium ion battery, the graphite electrode material as business electrode Typical Representative is wide
It is general to apply in the fields such as various electronic devices, electric car.The round-trip transition process of lithium ion will lead to the alternate body of electrode
Product expansion and contraction lead to the degradation in capacity and life time decay of graphite material so that corresponding strain/stress accumulation can be generated.
Therefore the diffusion process of lithium ion is very big to power-Electrochemical Performances of electrode, or even is related to the development of the following lithium battery
Trend.Intrinsic for commercial battery structure design, working electrode and generallys use aspectant frame mode to electrode, such as schemes
Shown in 1, the bulk between electrode is very narrow (100 μm or less), and can block working electrode to electrode, does not permit
Perhaps dispersal behavior of the optical measuring technique direct in-situ observation lithium ion in charge and discharge process, and then be also unfavorable for deeply probing into
Influence of the flooding mechanism to performances such as electrode of lithium cell capacity, service life.Therefore, for the research of lithium ion diffusion, in electrochemistry
Field is concerned, and designs a kind of electrode structure spread during the experiment convenient for in-situ observation, there is important science to grind
Study carefully meaning.Currently, have for in-situ observation lithium ion cell electrode reaction method, the electrode structure used be still in face of
The up-down structure mode in face, it is normal orientation along working electrode that the diffusion way of lithium ion is practical, and electrode structure is simultaneously non-critical
Edge-to-edge's form, and constraint type is complex, is not very convenient [1] to diffusion research.There are also other to study work
Make electrode design be it is rectangular, a kind of arrangement form is constituted with to electrode with one side of rectangular working electrode, but it only has studied
Diffusion [2] of the electrode in one-dimensional square, and the circular electrode applied in the shape of rectangular working electrode and real life
It has a certain difference, it cannot the more approximate vivid diffusion process for reflecting lithium ion.Therefore, it is badly in need of a kind of relatively simple
Electrode structural designs more approximately simulate lithium diffusion process in business electrode, in order to in-situ observation lithium ion is in electrochemistry
Real-time diffusion path in the process, and then certain basic design guidance is provided deeply to probe into propagation property mechanism.
Bibliography:
[1]J.Chen,A.K.Thapa,T.A.Berfield,In-situ characterization of strain
in lithium battery working electrodes,J.Power Sources 271(2014)406-413.
[2]Y.Qi,S.J.Harris,In Situ Observation of Strains during Lithiation
of a Graphite Electrode,J.Electrochem.Soc.157(2010)A741.
Summary of the invention
The main object of the present invention is to provide a kind of electrode knot that can be used for real-time in-situ observation lithium ion diffusion process
Structure, using circular working electrode structure, annular to electrode structure, constitute two electrodes by concentric circles position distribution in face
Edge-to-edge's structure type.
Technical scheme is as follows:
The electrode structure of lithium ion diffusion way in a kind of in-situ observation graphite material；It is to utilize circular working electrode knot
Structure, annular to electrode structure, constitute two electrodes by edge-to-edge's structure type of concentric circles position distribution in face；In electrode lithium from
The diffusion mode of son is along electrode radial manner.
The electrode structure, working electrode shape are circle, are annular to electrode shape, the internal diameter of annular electrode is wanted
Greater than the outer diameter of circular electrode；Electric installation uses the copper metal pin with flange, and top is pressed on electrode material,
Lower part is attached with conductive copper, realizes the connection of electrode material and outer lead.
In the electrode structure, metal pin is fixed therein heart position on the working electrode (s, realizes working electrode
Distribution of the upper electric field along electrode radial direction.
The electrode structure keeps metal pin at symmetrical annular spread the fixed of electrode, and quantity is even numbers.
It is described as follows:
The invention reside in by the diffusion mode of lithium ion in electrode by changing along electrode normal direction (vertical) mode as along electrode
Radial (level) mode, the design of electrode edge-to-edge's structure will not be set with the effect of contraction of complexity to working electrode in face, put
The big actual range of lithium ion diffusion, avoids block effect of the electrode to another electrode, is easy to real-time in-situ and sees
Survey the diffusion process of lithium ion.
Working electrode shape of the invention is circle, is annular to electrode shape, and the internal diameter of annular electrode is greater than circle
The outer diameter of electrode, the parameters such as unlimited fixed electrode material, size, thickness, it is other similar also；
Electric installation of the invention uses the copper metal pin with flange, and top is pressed on electrode material, lower part with
Conductive copper is attached, and is realized the connection of electrode material and outer lead, is easy to implement the charge-discharge test of electrode.
Metal pin of the invention is fixed therein heart position on the working electrode (s, realizes that electric field is along electrode on working electrode
Radial distribution, while playing the role of fixed working electrode, prevent its center from changing；
Fixation to electrode of the invention need to keep metal pin at symmetrical annular spread, and quantity is even numbers (at least 4
It is a), on the one hand guarantee that all directions synchronize conduction, on the other hand can preferably fix to electrode, guarantee itself and working electrode it
Between relatively accurate positional relationship.
The present invention can diffusion process to working electrode (such as graphite electrode) lithium ion in Li insertion extraction cyclic process into
The direct in-situ observation of row overcomes immeasurable difficulty caused by the face-to-face mode of traditional electrode, while the electricity proposed
Two electrodes are constituted the corresponding form of edge-to-edge by the frame mode that concentric circles relative position is arranged in pole-face, avoid complexity
Effect of contraction increases the diffusion length of lithium ion, is convenient for directly utilizing optical microscopy in-situ observation, while circular electrode
Design more meets the structure design of business electrode, can also realize that the diffusion in research all directions is developed.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of two traditional electrodes face arrangement modes；
Fig. 2 is the face annular arrangement schematic diagram of two electrode edge-to-edge's forms of the invention；
Fig. 3 is working electrode and the conductive structure and fixed form schematic diagram to electrode in the present invention；
Fig. 4 is the experimental image in situ of lithium ion diffusion profile in working electrode in the present invention.
Specific embodiment
Design process of the invention is further described below by way of specific embodiment, it should be noted that this implementation
Example be it is narrative, without being restrictive, do not limited the scope of protection of the present invention with this.
Structured design process in situ measurement electrode diffusion process is divided into following four part:
(1) preparation of electrode structure component
Used electrode structure component mainly includes working electrode (graphite electrode), to electrode (lithium electricity in this embodiment
Pole), conductive metal pin (copper product), conducting wire, electrode support, conductive copper etc., as shown in Figure 2 and Figure 3.Working electrode examination
Part is that graphite composite material is uniformly coated in copper foil current collector to made pellet electrode, it is to be prepared it is good after, using circle
Mould knife is cut on flake graphite electrode, and electrode shape is circle, and diameter dimension as needed can reasonable set.To electricity
Pole uses metal lithium electrode material, since working electrode is circular shape, needs to be designed as the shape of annular to electrode, to ensure
The annular internal edge of metal lithium electrode and the outer edge of graphite electrode are opposite.Therefore using slightly bigger than circular graphitic electrode size
Circular die knife carry out aperture in the centre of metal lithium electrode, make it that the annular shape that meets the requirements be presented.This implementation
Example uses the metal pin with flange, and be combined with conducting wire, conductive copper etc., collectively form the conductor wire of electrode interior
Road.
(2) working electrode and the arrangement to electrode position
As shown in figure 3, working electrode (graphite electrode) is placed on circular electrode support, to prevent the short of electrode
Road, the supporter is using the polytetrafluoroethylene material of insulation, and a micro hole is opened at position in its center, guarantees the gold on graphite electrode
Belonging to pin (taking d=2mm here) can pass through simultaneously and can be fitted close with electrode support.As shown in Fig. 2, due to electrode
(metal lithium electrode) is designed as annular, is stably placed at the outside of graphite electrode, guarantees that it is in close with graphite electrode
As concentric position, and keep in the same plane, to avoid electrode contact short circuit, needing that there are 1-2mm's between two electrodes
Gap.By putting for above-mentioned electrode, the face annular arrangement mode design of two electrode edge-to-edge's forms can be realized.
(3) working electrode and the design to electrodes conduct structure
Working electrode needs to design corresponding conductive structure, work electricity with concentric circles position pose pattern in the face to electrode
The conductive pin of pole is in center position, and it is right to be arranged in annular to conductive pin (even numbers amount) form in a center of symmetry of electrode
On electrode, to complete charge and discharge process with composite electrode.As shown in Fig. 2, firstly, for the graphite electrode that center is placed, due to setting
It is calculated as circular shape, to guarantee that the mode of lithium ion radially is spread, opens a small hole, hole in the center position of electrode
Then diameter about 2mm is passed through the small hole of electrode centers using the metallic conduction pin (copper product) with flange, utilizes it
The flange on top is pressed in the upper surface of electrode, in conjunction with the copper foil current collector of electrode lower part to realize electrode in upper and lower surface conduction
Consistency, so that it is guaranteed that the electrode relative uniformity that lithium ion is spread in a thickness direction.Secondly, for the circle of center opening
Lithium piece electrode, for the uniformity for guaranteeing annular all directions conduction, need to form symmetric form along ring since structure is annular design
Dispensing of conductive metal pin (generally even numbers, such as 4,6,8 ...) has the metal pins of flange in the present embodiment using 4
(copper product) is to meet the conduction needs of lithium electrode.4 metal pin upper flanges are pressed in the upper surface of electrode, lower part and one
A conductive copper carries out contact fixation, to realize metal lithium electrode conductive synchronism in all directions substantially, is convenient for lithium
The more orderly diffusion path along graphite electrode radial direction of ion is developed in real time.
(4) working electrode and fixation and constraint type to electrode
Used metal pin is also fixed electrode other than playing electric action in above-mentioned (3).Wherein graphite
The electrode is fixed on the centre on electrode support by metal pin by electrode, on the outer edge of graphite electrode, ring
The metal lithium electrode of shape equally uses metal pin to be fixed on electrode support, to keep two kinds of electrode relative positions
Accuracy.For constraint type, since only in centre, design has conductive pin to graphite electrode, and in the outer edge of electrode
Position is not provided with the effect of contraction of normal direction and circumferential load, is in electrode relatively freely without restrained condition.
In the embodiment, the diameter that graphite electrode uses is 12mm, and the internal diameter of annular metal lithium electrode is 15mm, and outer diameter is
The diameter of 20mm, metal pin are 2mm, and upper part lip diameter is about 4mm.
Electro-chemical test is carried out using electrode structure of the invention, loop test is carried out using the charge-discharge magnification of 0.2C,
The graphite electrode performance test of the structure carries out on Wuhan Jin Nuo Electronics Co., Ltd. cell tester.With time into
Lithium ion diffusion process can occur for row, electrode surface, be directed at graphite electrode constant duration acquisition electrode using optical microscopy
The lithium ion of surface image, recording electrode surface spreads information.The one of in-situ acquisition when Fig. 4 is lithium ion diffusion in experimentation
Electrode surface lithium ion distribution map is opened, the outer peripheral lithium ion content of circular work electrode is apparently higher than central area, and lithium
Ion is spread along radial distribution.The structure designs the circular electrode design closer to business, and can easily lead to
The real-time distribution that vision is directly observed lithium ion is crossed, without the laboratory apparatus of advanced valuableness, simple and effective, edge-to-edge
The easily studied electrode course of work of structure type in lithium ion diffusion process, experimental result can more fully, really
React the diffusion path and process of lithium ion.
The above description of this invention be it is illustrative and not restrictive, those skilled in the art understand, wanted in right
Ask it can be carried out within the spirit and scope of restriction it is many modification, variation or it is equivalent, but they fall within it is of the invention
In protection scope.
Claims (4)
1. the electrode structure of lithium ion diffusion way in a kind of in-situ observation graphite material；It is characterized in that utilizing circular work electricity
Pole structure, annular to electrode structure, constitute two electrodes by edge-to-edge's structure type of concentric circles position distribution in face；In electrode
The diffusion mode of lithium ion is along electrode radial manner.
2. electrode structure as described in claim 1, it is characterized in that working electrode shape is circle, it is annular to electrode shape,
The internal diameter of annular electrode is greater than the outer diameter of circular electrode；Electric installation uses the copper metal pin with flange, on
Portion is pressed on electrode material, and lower part is attached with conductive copper, realizes the connection of electrode material and outer lead.
3. electrode structure as claimed in claim 2, it is characterized in that metal pin is fixed therein heart position on the working electrode (s,
Realize that electric field is along the distribution of electrode radial direction on working electrode.
4. electrode structure as claimed in claim 2, it is characterized in that keeping metal pin at symmetrical annular the fixed of electrode
Distribution, quantity is even numbers.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114459963A (en) * | 2022-03-25 | 2022-05-10 | 蜂巢能源科技股份有限公司 | Method for evaluating lithium ion diffusion capacity in positive electrode material |
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| CN114459963B (en) * | 2022-03-25 | 2024-04-02 | 蜂巢能源科技股份有限公司 | Evaluation method for lithium ion diffusion capacity in positive electrode material |
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