CN109148827A - A kind of prelithiation method of electrode of lithium cell - Google Patents
A kind of prelithiation method of electrode of lithium cell Download PDFInfo
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- CN109148827A CN109148827A CN201811123668.XA CN201811123668A CN109148827A CN 109148827 A CN109148827 A CN 109148827A CN 201811123668 A CN201811123668 A CN 201811123668A CN 109148827 A CN109148827 A CN 109148827A
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- lithium
- pole piece
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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
- H01M4/139—Processes of manufacture
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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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- 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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- Manufacturing & Machinery (AREA)
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- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of prelithiation methods of electrode of lithium cell, belong to electrochemical field, comprising: step 1: battery pole piece and lithium metal being placed in inertia or low humidity low-oxygen environment and heated；Step 2: lithium metal being completed into the prelithiation of electrode of lithium cell in battery pole piece mantle friction under external force.This method is under inert gas protection; lithium metal is attached to electrode surface by external force and heat auxiliary; in a heated condition; soften with the lithium of battery pole piece contact position; it is easier to be adhered to electrode surface under external force; by lithium metal and battery pole piece friction treatment, a small amount of lithium is left in electrode surface, to realize the carry out prelithiation to battery.This method is implemented simple, is easy to be implanted in existing production line, and prelithiation degree is effectively controllable, can produce high capacity, high circulation, high magnification and the excellent lithium ion battery of security performance.
Description
Technical field
The invention belongs to electrochemical fields, and in particular to a kind of prelithiation method of electrode of lithium cell.
Background technique
Currently, lithium ion battery is answered extensively due to its higher energy density, good cyclical stability and security performance
For being developed rapidly in portable electronic product and power vehicle.But to the requirement of its specific capacity in these fields
Also higher and higher, current solution is concentrated mainly on the matching etc. of the electrode material and electrode material of research and development Fabrication of High Specific Capacitance.
But before battery several times in charge and discharge process can at electrode and electrolyte interface it is irreversible formed one layer it is solid
State electrolyte layer irreversible can should consume 5%~15% lithium ion in the process.So that for the first time coulombic efficiency reduce and
Battery capacity decline.So finding a kind of method can overcome the disadvantages that the specific volume to form lithium ion consumed by SEI film for improving battery
Amount, first charge-discharge coulombic efficiency and cyclical stability are particularly important.The main prelithiation method of current battery pole piece is as follows:
Application No. is the patent of JP1996027910 disclose it is a kind of metal lithium sheet is covered on negative battery pole piece,
Then it is wound, the method that lithium ion battery is made in fluid injection, encapsulation.Although this method can play the work to cathode prelithiation
With, but the amount of lithium piece used, far beyond the amount of lithium needed for pre- benefit lithium, the presence of extra lithium can generate Li dendrite, analysis lithium etc.
Phenomenon, there are biggish safety problems.
Publication No. CN1290209C patent application disclose it is a kind of inert metal lithium powder is mixed into negative electrode slurry, with realize
The method of prelithiation.But generally there is a protective layer on inertia lithium powder surface, needs external force that could squeeze out lithium.And by
Gently and the characteristics such as active in inertia lithium silty, it is easy to happen on fire or even explosion phenomenon in process.In addition, inertia lithium powder
To remaining space is had after battery pole piece lithiumation, reduces the compacted density of battery pole piece and increase the impedance of battery pole piece.
Publication No. CN105845894A patent application simultaneously discloses one kind under the effect of outer point source for lithium piece and electric battery
Pole piece connection, to reach prelithiation effect.But additional power source and new battery system, mechanism and mistake it have been related in this method
Journey is complicated.
Summary of the invention
In order to overcome the shortcomings of the prior art described above, the present invention provides a kind of prelithiation sides of electrode of lithium cell
Method.
To achieve the goals above, the invention provides the following technical scheme:
A kind of prelithiation method of electrode of lithium cell, step 1: battery pole piece and lithium metal being placed in inertia or low humidity is low
It is heated in oxygen environment；
Step 2: lithium metal being completed into the prelithiation of electrode of lithium cell in battery pole piece mantle friction under external force.
Preferably, the lithium metal in the step 1 is lithium piece, the one or more of lithium foil, lithium block, lithium band；Battery pole piece
For positive plate or negative electrode tab.
Preferably, the positive plate is cobalt acid lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, phosphoric acid
The one or more of vanadium lithium, sulphur/carbon composite, rich lithium base anode.
Preferably, the negative electrode tab is the one or more of graphite, silicon, silicon-carbon, metal oxide, sulfide, stannide.
Preferably, battery pole piece heating temperature is 50-180 DEG C in the step 1.
Preferably, the battery pole piece and lithium metal are placed in argon gas in the step 1 or humidity is less than the sky of 40ppm
It is heated in gas by air blower.
Preferably, lithium metal described in the step 2 is roll-in friction or plate in the battery pole piece mantle friction form
Pressure friction, the external force size being applied on the lithium metal are 0.5MPa-25MPa.
The prelithiation method of electrode of lithium cell provided by the invention under inert gas protection, will by external force and heat auxiliary
Lithium metal is attached to electrode surface, in a heated condition, softens with the lithium of battery pole piece contact position, is easier under external force
It is adhered to electrode surface, by lithium metal and battery pole piece friction treatment, a small amount of lithium is left in electrode surface, to realize to electricity
The carry out prelithiation in pond.This method is implemented simply, to be easy to be implanted in existing production line, and prelithiation degree is effectively controllable,
High capacity, high circulation, high magnification and the excellent lithium ion battery of security performance can be produced.
Detailed description of the invention
Fig. 1 is the schematic diagram for the rolling methods prelithiation that embodiment 1 and embodiment 2 provide；
Fig. 2 is the schematic diagram for the plate pressure method prelithiation that embodiment 3 provides；
Fig. 3 be comparative example and embodiment 1,2 and 3 prelithiation after full battery chemical property comparison diagram.
In figure, 1- lithium band, 2- lithium belt roller, 3- pole piece roller, the first battery pole piece of 4-, the second battery pole piece of 5-, 6- packet lithium pressure
Plate, 7- lithium piece, 8- pole piece plate, 9- chain extension bar.
Specific embodiment
With reference to the accompanying drawing, further description of the specific embodiments of the present invention.Following embodiment is only used for more
Technical solution of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
Embodiment 1
It is specific as shown in Figure 1, realizing the component of this method the present invention provides a kind of prelithiation method of electrode of lithium cell
Including lithium band 1, lithium belt roller 2, pole piece roller 3 and the first battery pole piece 4, lithium belt roller 2 and about 3 pole piece roller are oppositely arranged, and lithium band 1 twines
It is wound in lithium belt roller 2, the first battery pole piece 4 is wrapped on pole piece roller 3, and there are certain between lithium band 1 and the first battery pole piece 4
Gap, the distance between lithium belt roller 2 and pole piece roller 3 are adjustable, drive lithium belt roller 2 and pole piece roller 3 to rotate by motor, so that lithium band
1 and first battery pole piece 4 generate friction, specifically includes the following steps:
Step 1: battery pole piece and lithium metal being placed in inertia or low humidity low-oxygen environment and heated, specially lithium band 1 twines
It is wound in lithium belt roller 2, the first battery pole piece 4 is wrapped on pole piece roller 3, and there are certain between lithium band 1 and the first battery pole piece 4
Gap, it is specific adjustable between lithium belt roller 2 and pole piece roller 3；
Step 2: lithium metal is completed into the prelithiation of electrode of lithium cell in battery pole piece mantle friction under external force,
Specially adjusting the distance between lithium band 1 and the first battery pole piece 4 abuts the two, and motor drives lithium belt roller 2 and pole piece roller 3
It is rotated towards opposite direction, so that lithium band 1 is in 4 mantle friction of the first battery pole piece.
Lithium metal in step 1 is lithium piece, the one or more of lithium foil, lithium block, lithium band；Battery pole piece is positive plate or bears
Pole piece.
Further, positive plate is cobalt acid lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, vanadium phosphate
The one or more of lithium, sulphur/carbon composite, rich lithium base anode, negative electrode tab are graphite, silicon, silicon-carbon, metal oxide, vulcanization
The one or more of object, stannide.
In the present embodiment, the first battery pole piece 4 selects silicon-carbon cathode pole piece, by lithium band 1, lithium belt roller 2, and pole piece roller 3, first
Battery pole piece 4 is placed in the glove box full of argon gas.By adjusting lithium belt roller 2, the spacing adjusting of pole piece roller 3 is applied to lithium band 1
On pressure be 5MPa, 2 roller speed of lithium belt roller be 12r/min, 3 roller speed of pole piece roller be 20r/min, pass through resistance wire and thermocouple control
The temperature of pole piece roller processed is 80 DEG C, carries out prelithiation to pole piece with the mode of roll-in.
Embodiment 2
The present invention provides the prelithiation method of second of electrode of lithium cell, in the present embodiment, the component used and implementation
Example 1 is identical, the difference is that, the first battery pole piece 4 selects graphite cathode pole piece, by lithium band 1, lithium belt roller 2, and pole piece roller 3, the
One battery pole piece 4 is placed in the gloves phase full of argon gas.Spacing adjusting by adjusting lithium belt roller 2 and pole piece roller 3 is applied to lithium
The pressure taken is 1MPa, and lithium belt roller roller speed is 15r/min, and pole piece roller roller speed is 25r/min, passes through resistance wire and thermocouple control
The temperature of pole piece roller 3 processed is 100 DEG C, carries out prelithiation to pole piece with the mode of roll-in.Rest part is same as Example 1, this
In repeat no more.
Embodiment 3
It is specific as shown in Fig. 2, realizing the portion of this method the present invention provides the prelithiation method of the third electrode of lithium cell
Part includes the second battery pole piece 5, packet lithium pressing plate 6, lithium piece 7 and pole piece plate 8, and packet lithium pressing plate 6 and about 8 pole piece plate are oppositely arranged,
The setting of second battery pole piece 5 is arranged on 6 bottom surface of packet lithium pressing plate in 8 upper surface of pole piece plate, lithium piece 7, the second battery pole piece 5 and lithium
Certain gap is reserved between piece 7, and the distance between packet lithium pressing plate 6 and pole piece plate 8, including following step are adjusted by external force
It is rapid:
Step 1: battery pole piece and lithium metal being placed in inertia or low humidity low-oxygen environment and heated, specially the second battery
The setting of pole piece 5 is in 8 upper surface of pole piece plate, and lithium piece 7 is arranged on 6 bottom surface of packet lithium pressing plate, between the second battery pole piece 5 and lithium piece 7
Certain gap is reserved, the distance between packet lithium pressing plate 6 and pole piece plate 8 are adjusted by external force；
Step 2: lithium metal is completed into the prelithiation of electrode of lithium cell in battery pole piece mantle friction under external force,
It is equipped with a chain extension bar 9 specially on packet lithium pressing plate 6 and under pole piece plate 8, is clamped chain extension bar 9 using fixture, realizes packet lithium pressure
It on plate 6 and the pushing of pole piece plate 8 and lifts, so that driving lithium piece 7 in 5 mantle friction of the second battery pole piece.
Lithium metal in step 1 is lithium piece, the one or more of lithium foil, lithium block, lithium band；Battery pole piece is positive plate or bears
Pole piece.
Further, positive plate is cobalt acid lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, vanadium phosphate
The one or more of lithium, sulphur/carbon composite, rich lithium base anode, negative electrode tab are graphite, silicon, silicon-carbon, metal oxide, vulcanization
The one or more of object, stannide.
In the present embodiment, the second battery pole piece 5 selects NCM523 pole piece, by the second battery pole piece 5, packet lithium pressing plate 6, lithium piece
7 and pole piece plate 8 be placed in the glove box full of argon gas.The pressure for adjusting packet lithium pressing plate 6 is 2MPa, by adjusting the electricity in lower plate
It is 80 DEG C that resistance silk and thermocouple, which control its temperature, carries out prelithiation to pole piece with the mode of plate pressure.
A comparative example is selected, the battery that wherein comparative example is assembled for the electrode of not prelithiation, respectively by embodiment 1,2
With 3 prelithiation pole pieces with it is corresponding to electrode (prelithiation cathode to electrode be NCM523, prelithiation anode to electrode be silicon
Carbon anode) assembled battery is carried out, its chemical property is tested, test results are shown in figure 3, and abscissa is cycle-index, indulges and sits
Mark left and right is respectively specific capacity and coulombic efficiency, it is seen that embodiment 1,2 and 3 is after prelithiation, battery capacity and
Circulation conservation rate is all obviously improved, but 3 capacity of embodiment is low compared with Examples 1 and 2, is because embodiment 3 is using conventional friction, temperature
Spend lower, prelithiation degree deficiency.
Embodiment described above is merely preferred embodiments of the present invention, and the scope of protection of the present invention is not limited to this,
Anyone skilled in the art within the technical scope of the present disclosure, the technical solution that can be become apparent to
Simple change or equivalence replacement, all belong to the scope of protection of the present invention.
Claims (7)
1. a kind of prelithiation method of electrode of lithium cell, which comprises the following steps:
Step 1: battery pole piece and lithium metal being placed in inertia or low humidity low-oxygen environment and heated；
Step 2: lithium metal being completed into the prelithiation of electrode of lithium cell in battery pole piece mantle friction under external force.
2. the prelithiation method of electrode of lithium cell according to claim 1, which is characterized in that the metal in the step 1
Lithium is lithium piece, the one or more of lithium foil, lithium block, lithium band；Battery pole piece is positive plate or negative electrode tab.
3. the prelithiation method of electrode of lithium cell according to claim 2, which is characterized in that the positive plate is cobalt acid
Lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, phosphoric acid vanadium lithium, sulphur/carbon composite, rich lithium base anode
It is one or more of.
4. the prelithiation method of electrode of lithium cell according to claim 2, which is characterized in that the negative electrode tab be graphite,
The one or more of silicon, silicon-carbon, metal oxide, sulfide, stannide.
5. the prelithiation method of electrode of lithium cell according to claim 1, which is characterized in that battery pole in the step 1
Piece heating temperature is 50-180 DEG C.
6. the prelithiation method of electrode of lithium cell according to claim 1, which is characterized in that will be described in the step 1
Battery pole piece and lithium metal are placed in the air of argon gas or humidity less than 40ppm and are heated by air blower.
7. the prelithiation method of electrode of lithium cell according to claim 1, which is characterized in that lithium metal in the step 2
In the battery pole piece mantle friction form be roll-in friction or plate pressure friction, the external force size being applied on the lithium metal are
0.5MPa-25MPa。
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| CN201811123668.XA CN109148827A (en) | 2018-09-26 | 2018-09-26 | A kind of prelithiation method of electrode of lithium cell |
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| CN201811123668.XA CN109148827A (en) | 2018-09-26 | 2018-09-26 | A kind of prelithiation method of electrode of lithium cell |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111554883A (en) * | 2020-05-12 | 2020-08-18 | 郜明文 | Pre-lithiation method for preparing electrode membrane based on dry method |
| CN111952545A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Pre-lithiated lithium ion secondary battery negative electrode material and mechanical pre-lithiation method thereof |
| CN111952532A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Sodium ion secondary battery cathode material subjected to pre-sodium treatment and mechanical pre-sodium treatment method thereof |
| CN113678278A (en) * | 2019-05-10 | 2021-11-19 | 株式会社Lg新能源 | Method for preparing negative electrode |
| CN113851603A (en) * | 2021-09-10 | 2021-12-28 | 蜂巢能源科技有限公司 | Lithium pre-embedding method of negative plate, lithium pre-embedded negative plate and lithium ion battery |
| CN113948693A (en) * | 2021-09-23 | 2022-01-18 | 西安交通大学 | Lithium indium alloy cathode material for lithium battery and preparation method thereof |
| CN113972361A (en) * | 2020-07-24 | 2022-01-25 | 厦门稀土材料研究所 | Application of metal oxide/carbon intercalated layer two-dimensional composite material in lithium ion battery cathode material |
| CN114824175A (en) * | 2022-06-28 | 2022-07-29 | 宝晟(苏州)能源科技有限公司 | Sodium ion battery cathode pre-sodium treatment method for preparing electrode film based on dry method |
| CN115432753A (en) * | 2022-11-07 | 2022-12-06 | 宜宾锂宝新材料有限公司 | Positive electrode material, preparation method thereof and battery |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113678278A (en) * | 2019-05-10 | 2021-11-19 | 株式会社Lg新能源 | Method for preparing negative electrode |
| US12009502B2 (en) | 2019-05-10 | 2024-06-11 | Lg Energy Solution, Ltd. | Method of producing negative electrode |
| CN111952545A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Pre-lithiated lithium ion secondary battery negative electrode material and mechanical pre-lithiation method thereof |
| CN111952532A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Sodium ion secondary battery cathode material subjected to pre-sodium treatment and mechanical pre-sodium treatment method thereof |
| CN111952545B (en) * | 2019-05-16 | 2021-11-09 | 同济大学 | Pre-lithiated lithium ion secondary battery negative electrode material and mechanical pre-lithiation method thereof |
| CN111952532B (en) * | 2019-05-16 | 2021-11-09 | 同济大学 | Sodium ion secondary battery cathode material subjected to pre-sodium treatment and mechanical pre-sodium treatment method thereof |
| CN111554883B (en) * | 2020-05-12 | 2021-07-30 | 郜明文 | Pre-lithiation method for preparing electrode membrane based on dry method |
| CN111554883A (en) * | 2020-05-12 | 2020-08-18 | 郜明文 | Pre-lithiation method for preparing electrode membrane based on dry method |
| CN113972361A (en) * | 2020-07-24 | 2022-01-25 | 厦门稀土材料研究所 | Application of metal oxide/carbon intercalated layer two-dimensional composite material in lithium ion battery cathode material |
| CN113851603A (en) * | 2021-09-10 | 2021-12-28 | 蜂巢能源科技有限公司 | Lithium pre-embedding method of negative plate, lithium pre-embedded negative plate and lithium ion battery |
| CN113948693A (en) * | 2021-09-23 | 2022-01-18 | 西安交通大学 | Lithium indium alloy cathode material for lithium battery and preparation method thereof |
| CN114824175A (en) * | 2022-06-28 | 2022-07-29 | 宝晟(苏州)能源科技有限公司 | Sodium ion battery cathode pre-sodium treatment method for preparing electrode film based on dry method |
| CN115432753A (en) * | 2022-11-07 | 2022-12-06 | 宜宾锂宝新材料有限公司 | Positive electrode material, preparation method thereof and battery |
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Application publication date: 20190104 |