A kind of two-sided benefit lithium device of lithium ion battery negative electrode
Technical field
The utility model is related to a kind of two-sided benefit lithium devices of lithium ion battery negative electrode.
Background technology
With very big theoretical specific capacity when silicon is as lithium ion battery negative material, much larger than the theoretical ratio of graphite material
Capacity, exploitation silicon based anode material are of great significance for improving lithium ion battery energy density.But body after elemental silicon storage lithium
Product expansion is serious, causes the dusting of silicium cathode coating, comes off from collector, cycle life is very poor, without practical value.And silicon
When oxygen material makees lithium ion battery negative material, volume expansion problem after storage lithium can be substantially improved, but silica material
Efficiency only has about 70% for the first time, far below the efficiency for the first time (about 90%) of graphite material.In order to improve, efficiency for the first time is relatively low to ask
Topic supplements lithium metal as a kind of thinking on silica cathode, receives extensive approval.For mending the realization side of lithium on cathode
Method, domestic and international expert expand substantial amounts of exploration and practice, are below several frequently seen mode:
Application publication number is the patent of 102779975 A of CN:Feeding for storage lithium powder is set above cathode of lithium pole piece to be mended
Hopper, when implementing to mend lithium, lithium powder is adsorbed under electric field action on negative plate surface, then by roll-in lithium powder is made firmly to adhere to
On negative plate surface, so as to fulfill lithium is mended.This method can realize that it is lithium powder uniformly to mend the precondition of lithium in electrode surface
Grain wants that small and uniform, pressure roller surface smoothness is high, pressure roller should adhere to lithium powder less as far as possible.
Application publication number is the patent of 105489846 A of CN:By roll-in complex lithium band and lithium electrode to be mended, by lithium band
It adheres on lithium electrode to be mended, so as to form benefit lithium electrode, while the first base material as complex lithium ribbon matrix is removed, winding.
The practical precondition of this method is to obtain ultra-thin lithium band (thickness is generally less than 10 μm), the surface smoothness of pressure roller
It should be high (to avoid uneven).
Application publication number is the patent of 105702943 A of CN:The mixed-powder of negative material and conductive agent is first prepared, it will
Mixed-powder is packed into conductive hopper, and electrolyte to mixed-powder is added dropwise and infiltrates, electrolyte will be added dropwise using stainless steel gasket
Mixed-powder is compacted, and membrane is set in stainless steel gasket, gasket is set on membrane, sets lithium piece again on gasket, is passed through
All components are sealed by device, then sealing device are melted into using battery test system, so as to fulfill negative material
Pre- embedding lithium.
Application publication number is the patent of 204966620 U of CN:It is contacted, altogether for lithium device and cathode of lithium pole piece to be mended holding
With submergence in the electrolytic solution, due to for lithium device and cathode of lithium pole piece to be mended contact, possessing electron channel, and due to the two
Common submergence in the electrolytic solution, also has therebetween ion channel, mends the half-cell that lithium mechanism is equivalent to an internal short-circuit,
Lithium ion is deviate from from for lithium device, and electron reduction is obtained on cathode of lithium pole piece to be mended, therefore can realize benefit lithium.
Common several benefit lithium modes are enumerated above, to sum up, there is problems with:Using lithium powder mend the side of lithium
Formula is high to the uniformity requirements of lithium powder particles, and requires the surface smoothness of pressure roller high, is difficult in actual use
Ensure the exacting terms, lithium is of low quality so as to cause mending;Mode is crimped using ultra-thin lithium band, ultrathin metal lithium strip is at present simultaneously
It is not readily available, particularly requires the ultra-thin lithium band that thickness error is minimum, it is assumed that one layer 3 μm of lithium is mended, if some point is more
Go out 0.1 μm, which is bigger than average value by 3.33%, and the difficult point that lithium is mended using ultra-thin lithium band is to first have to obtain ultra-thin lithium
Band, even if solving the problems, such as the acquisition of ultra-thin lithium band, the problem of yet facing the easy fold of ultra-thin lithium band, easily be broken;Mend lithium
It needs to use electrolyte, it is dry or the problem of mend pole drying after lithium to resolve pre- embedding lithium powder.
In this context, it is very necessary to develop new benefit lithium technology.
Utility model content
The purpose of this utility model is to provide a kind of negative electrode of lithium ion battery simple and effective, benefit lithium is uniform and efficient
The two-sided benefit lithium device of pole piece.
To achieve the above object, the two-sided benefit lithium device of the lithium ion battery negative electrode of the utility model uses following skill
Art scheme:
Technical solution 1:The two-sided benefit lithium device of lithium ion battery negative electrode is included for banding cathode of lithium pole piece to be mended
The pole piece retractable volume mechanism of retractable volume, two sets of electricity including being used to carry out two winding shape solid electrolytes respectively retractable volume
Matter retractable volume mechanism is solved, two sets of lithium source retractables volume mechanism including being used to carry out two winding shape lithium sources respectively retractable volume, two
Set electrolyte retractable volume mechanism and two sets of lithium source retractable volume mechanisms are sequentially arranged in pole piece retractable volume mechanism both sides, so as to band
The both sides of shape cathode of lithium pole piece to be mended are followed successively by banding solid electrolyte and banding lithium source from inside to outside, mend lithium device and further include use
In the doubling roller for being bonded banding lithium source, solid electrolyte and cathode of lithium pole piece to be mended, mend lithium device and further include and be used for and banding
The anode power supply part of lithium source electrical connection and the cathode power supply part being electrically connected with cathode of lithium pole piece to be mended.The utility model provides one
Kind lithium ion battery negative electrode mends the new technology of lithium, is realized simultaneously by battery principle and mends lithium to cathode pole piece two sides, relatively
Lithium is mended in the ultra-thin lithium band pressing of easy broken belt, needs to solve the problems, such as mending lithium using electrolyte, being wanted to particle uniformity for drying
For seeking three kinds of technologies such as higher lithium powder benefit lithium, not only process is simple and efficient this technology, but also the quality of the product processed
It is higher, it has broad application prospects.
Technical solution 2:On the basis of technical solution 1, the doubling roller has two sets, is driven road positioned at unreeling structure respectively
The downstream in footpath and the upstream of rolling-up mechanism drive path, are equipped with more transition rollers between two sets of doubling rollers, transition roller with power supply just
Extremely it is connected, forms the anode power supply part.Banding lithium source, banding solid electrolyte, banding cathode of lithium pole piece to be mended are pooled to patch
Roller is closed, is fitted closely on doubling roller and transition roller.
Technical solution 3:On the basis of technical solution 2, the transition roller being capable of rotation.
Technical solution 4:On the basis of technical solution 2 or 3, cathode at least two pairs of part of power supply, a pair is arranged in pole piece
Between unreeling structure and first set doubling roller, another pair is arranged between pole piece rolling-up mechanism and second set of doubling roller.Lithium to be mended
Cathode pole piece by cathode power supply part realizes and is connected with power cathode that banding lithium source passes through anode power supply part realization and positive pole
Connection when banding lithium source, banding solid electrolyte and banding complex lithium ribbon matrix are in fitting winding on transition roller, mends lithium circuit
It is formed.
Technical solution 5:On the basis of technical solution 4, the diameter of row's transition roller in two rows of transition rollers is more than another
Arrange the diameter of transition roller.
Technical solution 6:On the basis of technical solution 1-3 any one, lithium source retractable volume mechanism, electrolyte retractable volume
Mechanism and pole piece retractable volume mechanism include:For retractable volume Scroll and unreeling shaft, for guiding deflector roll, be used for
The floating roller of tensioning.
Technical solution 7:On the basis of technical solution 6, the doubling roller includes doubling roller, when in use, banding lithium source,
Solid electrolyte and cathode of lithium pole piece to be mended are pooled on doubling roller simultaneously, and at doubling roller and transition roller realization patch
It closes.
Description of the drawings
Fig. 1 is the structure diagram of the embodiment 1 of the two-sided benefit lithium device of lithium ion battery negative electrode of the utility model;
Fig. 2 is the connection diagram of power supply and five layers of banding material in Fig. 1;
Fig. 3 is the schematic diagram of Fig. 2;
Fig. 4 is the structure diagram of the banding lithium source in embodiment 6;
In figure:1- banding lithium sources, 2- solid electrolytes, 3- cathode of lithium pole pieces to be mended, 4- unreeling shafts, 5- deflector rolls, 6- floating rollers,
7- doubling rollers, 8- positive conductive rollers, 9- negative conductive rollers, 10- Scrolls, 11- DC constant current power supplies, 20- lithium coating, 21- are copper-based
Body, A- are unreeled, and B- mends lithium, C- windings.
Specific embodiment
The embodiment of the utility model is described further below in conjunction with the accompanying drawings.
The embodiment 1 of the two-sided benefit lithium device of lithium ion battery negative electrode of the utility model:As shown in Figure 1, the application
It provides a kind of lithium ion battery negative electrode the two-sided continuous device for mending lithium, in addition to control system, further includes unreeling structure, mends lithium
Mechanism and rolling-up mechanism.Control system overall controlling device is run.Unreeling structure and rolling-up mechanism are for placement and with appropriate
Tension traction banding lithium source 1, solid electrolyte 2 and cathode of lithium pole piece 3 to be mended.Unreeling structure includes two sets of banding lithium source unreeling machines
Structure, two sets of banding solid electrolyte unreeling structures and a set of cathode of lithium pole piece unreeling structure to be mended, unreeling structure at least by
The components such as unreeling shaft 4, deflector roll 5, floating roller 6 are formed;Rolling-up mechanism includes two sets of banding lithium source rolling-up mechanisms, two sleeve solid electrolyte
Rolling-up mechanism and it is a set of mended cathode of lithium pole piece rolling-up mechanism, rolling-up mechanism is at least by deflector roll 5, floating roller 6, Scroll 10 etc.
Component is formed.Bu Li mechanisms are made of negative conductive roller 9, positive conductive roller 8, DC constant flowing power 11 and benefit lithium circuit etc.,
Wherein positive conductive roller 8 is connected with the anode of DC constant current power supply, and negative conductive roller 9 is connected with the cathode of DC constant current power supply.Cathode
Conductive rollers 9 are arranged on before first positive conductive roller 8 and after the last one positive conductive roller 8, that is to say in banding lithium source
1st, before solid electrolyte 2, cathode of lithium pole piece 3 to be mended collect and after separation.
Banding lithium source 1, solid electrolyte 2, wait mend cathode of lithium pole piece 3 after respective unreeling structure, at doubling roller 7
It pools together, into Bu Li mechanisms, is each wound into rolling-up mechanism after Bu Li mechanisms.
Under appropriate retractable volume tension, two sets of banding lithium sources 1, two sleeve solid electrolyte 2, a set of cathode of lithium pole piece to be mended
3 are closely fitted in the surface of positive conductive roller 8.When banding lithium source 1, solid electrolyte 2, cathode of lithium pole piece 3 to be mended are in anode
When 8 surface of conductive rollers fits closely, electron channel and lithium ion are provided simultaneously between banding lithium source 1 and cathode of lithium pole piece 3 to be mended
Passage is connected mend lithium circuit with this condition, and under electric field action, electronics flows to lithium to be mended from banding lithium source 1 by external circuit
Cathode pole piece 3, lithium ion are deviate from from banding lithium source 1, and through solid electrolyte 2, electronics is obtained also on cathode of lithium pole piece 3 to be mended
Original generates lithium metal, and lithium is mended so as to fulfill to cathode.
N (n is positive integer) a positive conductive roller 8 is set, and positive conductive roller 8 is connected with the anode of DC constant current power supply.
M (m is positive integer) a negative conductive roller 9 is set, it is preferred that m is >=2 natural number, it is furthermore preferred that m is >=4
Natural number, negative conductive roller 9 are connected with the cathode of DC constant current power supply.Positive conductive roller 8 and negative conductive roller 9 are conductive roll
Object, its electron resistivity is less than 10 under room temperature-3Ω·m.The roller diameter of positive conductive roller 8 and the roller diameter of negative conductive roller 9 can phases
It together, can not also be identical;The roller diameter of each positive conductive roller 8 can be identical, can not also be identical;The roller diameter of each negative conductive roller 9
Can be identical, it can not also be identical.Positive conductive roller 8 and negative conductive roller 9 can be with rotations, in favor of banding lithium source 1, solid electricity
Solve matter 2,3 retractable volume of cathode of lithium pole piece to be mended.Setting can transmit the solid electrolyte 2 of lithium ion to separate (or connection) banding
Lithium source 1 and cathode of lithium pole piece 3 to be mended, the ionic conductivity under 2 room temperature of solid electrolyte is more than 10-7S/cm, it is preferred that Gu
Ionic conductivity under 2 room temperature of body electrolyte is more than 10-4S/cm.Banding lithium source 1 be metal lithium bands, complex lithium band either lithium from
Sub- anode.Banding lithium source 1, solid electrolyte 2, cathode of lithium pole piece 3 to be mended all are ribbons, can be carried out retractable volume behaviour
Make.
In the present embodiment:(1) 4 negative conductive rollers 9 and 275 positive conductive rollers 8, each 9 diameter of negative conductive roller are set
It is 150mm, 9 present position of negative conductive roller is as shown in Figure 1;Positive conductive roller 8 is divided to for diameter 100mm and diameter 150mm two
A specification, wherein 138, diameter 100mm positive conductives roller, 137, diameter 150mm positive conductives roller, two neighboring diameter
The axle center spacing 200mm of 100mm positive conductives roller 8, the axle center of diameter 150mm positive conductives roller 8 are straight to adjacent thereto two
The distance of 8 axial connecting line of footpath 100mm positive conductives roller is 175mm.By this set, lithium length is effectively mended in entire Bu Li areas
About 60m;
(2) 3 width 84mm of cathode of lithium pole piece to be mended, one side coating amount 4.5mg/cm2(activity substance content 94%, specific capacity
680mAh/g, capacity per unit area about 2.876mAh/cm2, active material efficiency 70% for the first time);
(3) solid electrolyte film selects Li1.4Al0.4Ti1.6(PO4)3LISICON types inorganic solid electrolyte 2, the lithium of material
Ionic conductivity is 1.12 × 10-3S/cm, thickness 0.030mm, width 110mm;
(4) banding lithium source 1 is width 100mm, the metal lithium bands of thickness 0.150mm;
(5) DC constant current power supply setting electric current value 1712A, banding lithium source 1, solid electrolyte 2 and cathode of lithium pole piece 3 to be mended
Tape running speed is 20m/min.
The application uses banding lithium source 1, avoids, using the huge lithium powder of specific surface area, greatly reducing security risk.Band
Shape lithium source 1 can be metal lithium bands (needing not be ultrathin metal lithium strip, can use 200 μm of even thicker lithium bands), can also
It is complex lithium band, can also be lithium ion cell positive.The application uses solid electrolyte 2, avoids using electrolyte.This side
Case be advantageous in that avoid mend lithium after pole piece need the problem of dry.
The present apparatus realizes that the principle for mending lithium is that banding lithium source 1, solid electrolyte 2, cathode of lithium pole piece 3 to be mended are formed one
The all solid state half-cell (during using metal lithium bands or complex lithium band as lithium source) or all-solid-state battery of a open type are (with lithium-ion electric
Pond just extremely lithium source when);Then, to all solid state half-cell (or all-solid-state battery) the control current discharge (or charging).
Embodiment 2:The present embodiment and embodiment 1 the difference is that, DC constant current power supply setting electric current value 1712A, band
The tape running speed of shape lithium source, solid electrolyte and cathode of lithium to be mended is 40m/min.
Embodiment 3:The present embodiment and embodiment 1 the difference is that, DC constant current power supply setting electric current value 1712A, band
The tape running speed of shape lithium source, solid electrolyte and cathode of lithium to be mended is 60m/min.
Embodiment 4:The present embodiment and embodiment 1 the difference is that, DC constant current power supply setting electric current value 3424A, band
The tape running speed of shape lithium source, solid electrolyte and cathode of lithium to be mended is 40m/min.
Embodiment 5:The present embodiment and embodiment 1 the difference is that, DC constant current power supply setting electric current value 5136A, band
The tape running speed of shape lithium source, solid electrolyte and cathode of lithium to be mended is 60m/min.
Embodiment 6:The present embodiment and embodiment 1 the difference is that, banding lithium source is width 100mm, total thickness 0.150mm
Complex lithium band, complex lithium band be the copper foil using 0.010mm thickness as matrix, i.e. Copper substrate 21, one layer of 0.140mm thickness of copper foil overlying
Lithium layer, i.e. lithium coating 20, structure is as shown in Figure 4.
Embodiment 7:The present embodiment and embodiment 1 the difference is that, banding lithium source is width 100mm, one side coating amount
For 17mg/cm2Lithium cobaltate cathode.
Embodiment 8:The present embodiment and embodiment 1 the difference is that, banding lithium source is width 100mm, one side coating amount
For 15mg/cm2Lithium manganate cathode.
Embodiment 9:The present embodiment and embodiment 1 the difference is that, banding lithium source is width 100mm, one side coating amount
For 15mg/cm2Iron phosphate lithium positive pole.
Embodiment 10:The present embodiment and embodiment 1 the difference is that, banding lithium source is width 100mm, one side coating amount
For 17mg/cm2Lithium nickel cobalt manganese oxide (ternary) anode.
Embodiment 11:The present embodiment and embodiment 1 the difference is that, solid electrolyte film selects width 110mm, thickness
Ionic conductivity is 7.5 × 10 when spending 50 μm, 30 DEG C-4The modified PE O based polyalcohol solid electrolytes of S/cm.
Embodiment 12:The present embodiment and embodiment 1 the difference is that, 4 negative conductive rollers and 137 anodes are set
Conductive rollers, each negative conductive roller diameter is 150mm;Positive conductive roller is divided to diameter 100mm and diameter 150mm two specifications,
Middle 69, diameter 100mm positive conductives roller, 68, diameter 150mm positive conductives roller, two neighboring diameter 100mm positive conductive rollers
Axle center spacing 200mm, the axle center of each diameter 150mm positive conductive rollers to two diameter 100mm positive conductives adjacent thereto
The distance of roller axial connecting line is 175mm.By this set, it is about 30m effectively to mend lithium length in entire Bu Li areas.Direct current constant current
Source setting electric current value 856A, banding lithium source, solid electrolyte and cathode of lithium tape running speed to be mended are 10m/min.
Each embodiment is mended after lithium the cathode that obtains and do not mend cathode of lithium and (as a comparison case) cuts into 990mm's long
Cathode section (width 84mm), with anode (wide 80mm, long 922mm, one side coating amount 18.7mg/cm2, activity substance content 96%,
Capacity per unit area 2.713mAh/cm2, positive electrode active materials efficiency 88% for the first time), lug, membrane, plastic-aluminum shell, electrolyte etc.
By welding, winding, top side seal, fluid injection, the processes such as chemical conversion be fabricated to flexible packing lithium ion electric core, count its first charge-discharge effect
Rate and constant volume capacity are as follows:
Embodiment |
Efficiency for the first time |
Constant volume capacity (mAh) |
Comparative example |
60.02% |
2728.2 |
Embodiment 1 |
87.52% |
3978.2 |
Embodiment 2 |
73.77% |
3353.2 |
Embodiment 3 |
69.19% |
3145.0 |
Embodiment 4 |
87.51% |
3977.7 |
Embodiment 5 |
87.51% |
3977.7 |
Embodiment 6 |
87.52% |
3978.2 |
Embodiment 7 |
87.51% |
3977.7 |
Embodiment 8 |
87.52% |
3978.2 |
Embodiment 9 |
87.52% |
3978.2 |
Embodiment 10 |
87.52% |
3978.2 |
Embodiment 11 |
87.51% |
3977.7 |
Embodiment 12 |
87.51% |
3977.7 |
The experimental results showed that the device can effectively be implemented to mend lithium, and by adjusting size of current, tape running speed energy
Lithium amount is mended in quantitative control.