CN110518189A - It is a kind of at the same realize to positive electrode pre-deoxidation, to the device and method of negative electrode material prelithiation - Google Patents
It is a kind of at the same realize to positive electrode pre-deoxidation, to the device and method of negative electrode material prelithiation Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
It is a kind of at the same realize to positive electrode pre-deoxidation, to the device and method of negative electrode material prelithiation, belong to field of lithium ion battery.The present invention carries out charge and discharge electric treatment, lithium extra in lithium-rich oxide anode material is used for the prelithiation of silicon class negative electrode material, realize resource reutilization by matching lithium-rich oxide anode material with silicon class negative electrode material.Present invention process is simple, can be realized simultaneously the pre-deoxidation to positive electrode and the pre- lithium to negative electrode material, low in cost, is produced on a large scale.
Description
Technical field
The invention belongs to lithium ion battery electrode material fields, and in particular to a kind of to realize simultaneously to positive electrode pre-deoxidation
Change, to the device and method of negative electrode material prelithiation.
Background technique
Currently, gradually prohibiting selling with fuel vehicle, lithium ion battery has occupied the mainstream market of electric car, electronic vapour
The fast development of vehicle proposes increasingly higher demands to the energy density of lithium ion battery.Traditional positive and negative electrode material is
It is not able to satisfy the electric automobile market of high speed development gradually, needs to develop novel lithium ion battery positive and negative electrode material.Rich lithium layer
Shape oxide anode material is gradually studied because of advantages such as its high specific discharge capacity (> 250mAh/g), high security, low costs
The concern of personnel is one of potential next-generation anode material for lithium-ion batteries.Meanwhile silicon class negative electrode material Yin Qigao is put
Electric specific capacity (~ 2000mAh/g, much larger than 400 ~ 600mAh/g of current commercialization negative electrode material), it has also become lithium ion battery
Fall over each other the object of research with layout in negative electrode material field.
But lithium-rich oxide anode material is because of its high rate performance is poor, cycle life is low, voltage declines the problems such as dropping limit
Its commercial applications is made.In particular, lithium-rich oxide anode material first circle efficiency for charge-discharge is low, a large amount of lithium is not effectively reversible
Ground returns to anode, i.e. first circle will cause a large amount of active lithium loss, subsequent to be applied.The part lithium continues to stay in negative
In the material of pole, the waste of matched negative electrode material is also led to, and reduces the energy density of full battery.Moreover, rich lithium layer
In shape oxide material first circle formation process, part of oxygen precipitation is had, the erosion to electrolyte is caused, it is caused to recycle the longevity
Life is further low.Therefore, how to reduce or avoid lithium-rich oxide material first circle lithium resource waste and how
Erosion of the oxygen for avoiding first circle from being precipitated to electrolyte, is that commercial applications must solve the problems, such as.
On the other hand, the problems such as first charge-discharge efficiency of silicon class negative electrode material is low, cyclical stability is poor not can solve yet.
Silicon class negative electrode material has embedding lithium site abundant, still, after lithium ion insertion, the abjection that some lithium is not effectively reversible, but
It is trapped in negative electrode material, becomes " dead " lithium, lose activity.Cause the first charge-discharge efficiency of material low, and lithium is caused to provide
A large amount of wastes in source, reduce the energy density of entire full battery indirectly.Therefore, it in order to promote the energy density of full battery, needs
Prelithiation is carried out to negative electrode material, improves its head effect.
Prelithiation technique is to solve electrode material head to imitate effective ways that are low, improving full battery energy density.Lithium-ion electric
In the formation process of pond, or due to forming consumption of the SEI film to Li, or due to electrode material itself caused by activity Li mistake
It is living, it can all cause the capacitance loss of lithium ion battery.Electrode material prelithiation can be supplemented in battery cyclic process for the first time
Irreversible capacity loss is conducive to the raising of battery cycle life and the promotion of energy density.
Currently, the method for prelithiation is mainly lithium metal (such as lithium powder, lithium piece) to the pre- lithium of cathode, this method not only wastes lithium
Resource, and to operating environment requirements harshness, investment is big, more easily causes security risk, it is urgent to provide a kind of safety, saves, easily
The novel prelithiation method of operation.
In the related technology, different researcher's method therefors are different, but all deposit some high production cost, and working environment is severe
The problems such as at quarter, effect is not significant.Therefore, in current research and production, it is required to a kind of resource-effective, simple process, it is raw
Produce at low cost, the impact of performance is significant, can be can be realized simultaneously with one kind of large-scale production to positive electrode pre-deoxidation, to negative
The device and method of pole material prelithiation.
Summary of the invention
In order to solve, lithium-rich oxide anode material and silicon class negative electrode material first circle efficiency for charge-discharge be low, cycle performance
The problems such as poor, the present invention invented a kind of realization simultaneously to positive electrode pre-deoxidation, to the device of negative electrode material prelithiation and
Method.
The device and method can be realized simultaneously the pre-deoxidation to positive electrode and the pre- lithium to negative electrode material
Change.
The positive electrode is lithium-rich oxide anode material, and the negative electrode material includes Si, SiOx, Si-
C compound, SiOx-C compound.
The device includes working bin, the electrolyte in working bin, protective cover, biography to the device of the invention as shown in Figure 1:
Dynamic device and power supply unit；The protective cover is divided into protective cover A and protective cover B, and is connected to respectively with working bin left and right ends,
It is set on protective cover A there are two door, i.e. positive plate entrance and negative electrode tab entrance, sets that there are two doors, i.e. positive plate on protective cover B
Outlet and negative electrode tab outlet；The transmission device is divided into transmission device A and transmission device B, and transmission device A includes that positive plate is put
Volume, positive plate winding and several positive plate transmission gears, transmission device B include that negative electrode tab unreels, negative electrode tab is wound and several negative
Pole piece transmission gear, transmission device A and transmission device B can be such that positive/negative plate is driven between protective cover and working bin respectively；
The power supply unit includes charge and discharge power supply, conducting wire and power supply gear；The power supply gear is divided into power supply gear A and power supply tooth
B is taken turns, and is connected respectively with charge and discharge two poles by conducting wire.The electrolyte is Li salt/organic solvent electrolyte.It is described
Charge and discharge power supply different voltage and electric current can be set according to demand.The power supply gear A and power supply gear B are respectively and just
Pole pole piece and cathode pole piece are in contact, and do not influence the normal work of transmission device.
Specific work steps of the invention is as follows:
(1) positive electrode sized mixing, be coated with etc. and preparing anode pole piece, and being wound into a roll；Negative electrode material is sized mixing, is applied
Cloth etc. prepares cathode pole piece, and is wound into a roll；
(2) coiled anode pole piece is fed from positive plate entrance, is carried on transmission device A；Certainly by coiled cathode pole piece
The charging of negative electrode tab entrance, is carried on transmission device B；
(3) start transmission device A and transmission device B, positive plate volume and negative electrode tab volume unreel respectively, positive and negative electrode pole piece transmitted
Enter in electrolyte, stops transmission；
(4) charge and discharge power supply is connected, charge and discharge electric treatment is carried out, after charge and discharge, disconnects charge and discharge power supply；
(5) transmission device A and transmission device B continue to be driven, and transmission distance is respectively LAAnd LB, stop transmission.Repeat step 4；
(6) charge and discharge treated anode pole piece and cathode pole piece are wound at positive plate winding and negative electrode tab winding respectively；
(7) the positive/negative plate volume after winding respectively obtains pre-deoxidation respectively from positive plate outlet and negative electrode tab outlet outflow
The cathode pole piece of anode pole piece and prelithiation.
In above-mentioned work step (4), the charge and discharge electric treatment, which refers to, first charges to positive and negative anodes pole piece, then discharges, charging
Blanking voltage is 4.6 ~ 4.8V, and discharge cut-off voltage is 0.1 ~ 2V, and charging and discharging currents density is 1mA/g ~ 1000mA/g.
In above-mentioned work step (5), the transmission distance LARefer to the length for immersing the anode pole piece of anolyte portion；
The transmission distance LBRefer to the length for immersing the cathode pole piece of anolyte portion；The anode of the immersion anolyte portion
The length of pole piece and the length of cathode pole piece, can by manufacturing tortuous, circuitous in electrolyte, to increase length,
It improves efficiency.
The invention has the following beneficial effects:
(1) lithium-rich oxide anode material is in first circle charge and discharge process, some lithium is not due to material itself
Anode can be returned to, is still trapped in negative electrode material.And silicon class negative electrode material is in first circle charge and discharge process, due to material itself
Property, a part of active lithium can be trapped in negative electrode material, lose activity.The present invention is by by lithium-rich oxide anode material
Material is matched with silicon class negative electrode material, carries out charge and discharge electric treatment, lithium extra in lithium-rich oxide anode material is used for silicon
The prelithiation of class negative electrode material realizes resource reutilization；
(2) lithium-rich oxide anode material avoids erosion of the precipitated oxygen to electrolyte after pre-deoxidationization processing,
To greatly prolong its cycle life；
(3) after carrying out prelithiation processing to silicon class negative electrode material, the energy density of its full battery can be greatly improved；
(4) present invention process is simple, can be realized simultaneously the pre-deoxidation to positive electrode and the pre- lithium to negative electrode material, at low cost
Honest and clean, a step is completed；
(5) the positive and negative anodes pole piece after process through the invention, obvious reliable, the environmentally friendly, product quality of performance boost
It is uniform, reproducible, be produced on a large scale.
Detailed description of the invention
Fig. 1: the device of the invention figure.In figure: 1-working bin；2-electrolyte；3-protective cover A；4-protective cover B；5—
Transmission device A；6-transmission device B；7-power supply units；31-positive plate entrances；32-negative electrode tab entrances；41-positive plates go out
Mouthful；The outlet of 42-negative electrode tabs；51-positive plates unreel；52-positive plate transmission gears；The winding of 53-positive plates；61-cathode
Piece unreels；62-negative electrode tab transmission gears；The winding of 63-negative electrode tabs；71-charge and discharge power supplys；72-power supply gear Bs；73-power supplies
Gear A；74-conducting wires.
Fig. 2: Li in the embodiment of the present invention 11.2Mn0.54Ni0.13Co0.13O2C-V(specific capacity-electricity of/graphite full battery
Pressure) curve.
Fig. 3: C-V(specific capacity-voltage of SiOx-C/Li button cell in the embodiment of the present invention 1) curve.
Fig. 4: Li in comparative example of the invention1.2Mn0.54Ni0.13Co0.13O2C-V(specific capacity-electricity of/graphite full battery
Pressure) curve.
Fig. 5: C-V(specific capacity-voltage of SiOx-C/Li button cell in comparative example of the invention) curve.
Fig. 6: Li in comparative example and embodiment 1 of the invention1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery is at 0.5C times
Cycle performance under rate.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this
Inventive technique scheme is modified or equivalent replacement, without departing from the principle and range of technical solution of the present invention, should cover
Within the protection scope of the present invention.
Embodiment 1
By Li1.2Mn0.54Ni0.13Co0.13O2Positive electrode, which is sized mixing, is coated with etc., prepares anode pole piece, and is wound into a roll；It will
SiOx-C negative electrode material, which is sized mixing, is coated with etc., prepares cathode pole piece, and is wound into a roll.By what is prepared
Li1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and SiOx-C cathode pole piece are handled according to Fig. 1 shown device.It will prepare
Anode pole piece from positive plate entrance feed, be carried on transmission device A；By the cathode pole piece prepared from negative electrode tab entrance into
Material, is carried on transmission device B；Anode pole piece and cathode pole piece are sent into electrolyte (LiPF6 (1mol/L) by transmission device respectively
/ EC+DEC (1:1)) in, then stop transmission；Charge and discharge power supply is connected, charge and discharge electric treatment is carried out to positive and negative anodes pole piece, is first charged,
Setting charge cutoff voltage is 4.7V, then is discharged, and discharge cut-off voltage 0.1V, charging and discharging currents density is both configured to 10mA/
g；After charge and discharge, charge and discharge power supply is cut off, anode pole piece and cathode pole piece spread out of electrolyte by transmission device respectively, and
It is wound at winding；Finally respectively obtain the Li of pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2The SiOx-C of anode pole piece and prelithiation
Cathode pole piece.
By the Li of obtained pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and commercial graphite cathode pole piece carry out
Matching (cathode excessive 5%) is cut respectively, is weighed, vacuum outgas, fluid injection, sealing etc., being prepared
Li1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery.
The SiOx-C pole piece of obtained prelithiation is assembled into button cell together with Li piece, obtains SiOx-C/Li button
Battery.
The Li of preparation1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery, C-V(specific capacity-voltage) curve such as Fig. 2 institute
Show, first circle charge specific capacity is 275.65mAh/g, and first circle specific discharge capacity is 267.99mAh/g, and efficiency for charge-discharge is
97.22%。
The SiOx-C/Li button cell of preparation, C-V(specific capacity-voltage) curve as shown in figure 3, first circle discharge specific volume
Amount is 1350.22mAh/g, and first circle charge specific capacity is 1310.17mAh/g, efficiency for charge-discharge 97.03%.
Embodiment 2
The Li that will be prepared1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and SiOx-C cathode pole piece are carried out according to Fig. 1 shown device
Processing.The anode pole piece prepared is fed from positive plate entrance, is carried on transmission device A；Certainly by the cathode pole piece prepared
The charging of negative electrode tab entrance, is carried on transmission device B；Anode pole piece and cathode pole piece pass through transmission device respectively and are sent into electrolyte
In (LiPF6 (1mol/L)/EC+DEC (1:1)), then stop transmission；Charge and discharge power supply is connected, positive and negative anodes pole piece is filled
Discharge treatment first charges, and setting charge cutoff voltage is 4.6V, then is discharged, discharge cut-off voltage 0.1V, and charging and discharging currents are close
Degree is both configured to 1000mA/g；After charge and discharge, charge and discharge power supply is cut off, anode pole piece and cathode pole piece pass through transmission dress respectively
Outflow electrolyte is set, and is wound at winding；Finally respectively obtain the Li of pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Positive pole
The SiOx-C cathode pole piece of piece and prelithiation.
By the Li of obtained pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and commercial graphite cathode pole piece carry out
Matching (cathode excessive 5%) is cut respectively, is weighed, vacuum outgas, fluid injection, sealing etc., being prepared
Li1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery.
The SiOx-C pole piece of obtained prelithiation is assembled into button cell together with Li piece, obtains SiOx-C/Li button
Battery.
The Li of preparation1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery, first circle charge specific capacity is 263.82mAh/g, first
Circle specific discharge capacity is 245.05mAh/g, efficiency for charge-discharge 92.88%.
The SiOx-C/Li button cell of preparation, first circle specific discharge capacity are 1316.91mAh/g, and first circle charge specific capacity is
1245.59mAh/g efficiency for charge-discharge 94.58%.
Embodiment 3
The Li that will be prepared1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and SiOx-C cathode pole piece are carried out according to Fig. 1 shown device
Processing.The anode pole piece prepared is fed from positive plate entrance, is carried on transmission device A；Certainly by the cathode pole piece prepared
The charging of negative electrode tab entrance, is carried on transmission device B；Anode pole piece and cathode pole piece pass through transmission device respectively and are sent into electrolyte
In (LiPF6 (1mol/L)/EC+DEC (1:1)), then stop transmission；Charge and discharge power supply is connected, positive and negative anodes pole piece is filled
Discharge treatment first charges, and setting charge cutoff voltage is 4.8V, then is discharged, discharge cut-off voltage 2V, charging and discharging currents density
It is both configured to 1mA/g；After charge and discharge, charge and discharge power supply is cut off, anode pole piece and cathode pole piece are passed by transmission device respectively
Electrolyte out, and wound at winding；Finally respectively obtain the Li of pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and
The SiOx-C cathode pole piece of prelithiation.
By the Li of obtained pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and commercial graphite cathode pole piece carry out
Matching (cathode excessive 5%) is cut respectively, is weighed, vacuum outgas, fluid injection, sealing etc., being prepared
Li1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery.
The SiOx-C pole piece of obtained prelithiation is assembled into button cell together with Li piece, obtains SiOx-C/Li button
Battery.
The Li of preparation1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery, first circle charge specific capacity is 261.44mAh/g, first
Circle specific discharge capacity is 252.96mAh/g, efficiency for charge-discharge 96.76%.
The SiOx-C/Li button cell of preparation, first circle specific discharge capacity are 1329.11mAh/g, and first circle charge specific capacity is
1216.36mAh/g efficiency for charge-discharge 91.51%.
Embodiment 4
The Li that will be prepared1.18Mn0.492Ni0.164Co0.164O2Anode pole piece and SiOx-C cathode pole piece are according to Fig. 1 shown device
It is handled.The anode pole piece prepared is fed from positive plate entrance, is carried on transmission device A；The cathode pole that will be prepared
Piece is fed from negative electrode tab entrance, is carried on transmission device B；Anode pole piece and cathode pole piece are sent by transmission device respectively to be electrolysed
In liquid (LiPF6 (1mol/L)/EC+DMC (1:1)), then stop transmission；Charge and discharge power supply is connected, positive and negative anodes pole piece is carried out
Charge and discharge electric treatment, first charges, and setting charge cutoff voltage is 4.7V, then is discharged, discharge cut-off voltage 0.1V, charging and discharging currents
Density is both configured to 10mA/g；After charge and discharge, charge and discharge power supply is cut off, anode pole piece and cathode pole piece pass through transmission dress respectively
Outflow electrolyte is set, and is wound at winding；Finally respectively obtain the Li of pre-deoxidation1.18Mn0.492Ni0.164Co0.164O2Anode
The SiOx-C cathode pole piece of pole piece and prelithiation.
By the Li of obtained pre-deoxidation1.18Mn0.492Ni0.164Co0.164O2Anode pole piece and commercial graphite cathode pole piece into
Row matching (cathode excessive 5%) is cut respectively, is weighed, vacuum outgas, fluid injection, sealing etc., being prepared
Li1.18Mn0.492Ni0.164Co0.164O2/ graphite full battery.
The SiOx-C pole piece of obtained prelithiation is assembled into button cell together with Li piece, obtains SiOx-C/Li button
Battery.
The Li of preparation1.18Mn0.492Ni0.164Co0.164O2/ graphite full battery, first circle charge specific capacity are 273.90mAh/g,
First circle specific discharge capacity is 265.07mAh/g, efficiency for charge-discharge 96.78%.
The SiOx-C/Li button cell of preparation, first circle specific discharge capacity are 1346.52mAh/g, and first circle charge specific capacity is
1305.23mAh/g efficiency for charge-discharge 96.93%.
Embodiment 5
The Li that will be prepared1.18Mn0.492Ni0.164Co0.164O2Anode pole piece and Si-C cathode pole piece according to Fig. 1 shown device into
Row processing.The anode pole piece prepared is fed from positive plate entrance, is carried on transmission device A；The cathode pole piece that will be prepared
It is fed from negative electrode tab entrance, is carried on transmission device B；Anode pole piece and cathode pole piece pass through transmission device respectively and are sent into electrolyte
In (LiPF6 (1mol/L)/EC+DMC (1:1)), then stop transmission；Charge and discharge power supply is connected, positive and negative anodes pole piece is filled
Discharge treatment first charges, and setting charge cutoff voltage is 4.8V, then is discharged, discharge cut-off voltage 1V, charging and discharging currents density
It is both configured to 1mA/g；After charge and discharge, charge and discharge power supply is cut off, anode pole piece and cathode pole piece are passed by transmission device respectively
Electrolyte out, and wound at winding；Finally respectively obtain the Li of pre-deoxidation1.18Mn0.492Ni0.164Co0.164O2Anode pole piece
With the SiOx-C cathode pole piece of prelithiation.
By the Li of obtained pre-deoxidation1.18Mn0.492Ni0.164Co0.164O2Anode pole piece and commercial graphite cathode pole piece into
Row matching (cathode excessive 5%) is cut respectively, is weighed, vacuum outgas, fluid injection, sealing etc., being prepared
Li1.18Mn0.492Ni0.164Co0.164O2/ graphite full battery.
The Si-C pole piece of obtained prelithiation is assembled into button cell together with Li piece, obtains Si-C/Li button cell.
The Li of preparation1.18Mn0.492Ni0.164Co0.164O2/ graphite full battery, first circle charge specific capacity are 271.38mAh/g,
First circle specific discharge capacity is 262.03mAh/g, efficiency for charge-discharge 96.55%.
The Si-C/Li button cell of preparation, first circle specific discharge capacity are 1389.18mAh/g, and first circle charge specific capacity is
1326.60mAh/g efficiency for charge-discharge 95.50%.
Embodiment 6
The Li that will be prepared1.18Mn0.492Ni0.164Co0.164O2Anode pole piece and SiOx cathode pole piece according to Fig. 1 shown device into
Row processing.The anode pole piece prepared is fed from positive plate entrance, is carried on transmission device A；The cathode pole piece that will be prepared
It is fed from negative electrode tab entrance, is carried on transmission device B；Anode pole piece and cathode pole piece pass through transmission device respectively and are sent into electrolyte
In (LiPF6 (1mol/L)/EC+DEC+EMC (1:1:1)), then stop transmission；Charge and discharge power supply is connected, to positive and negative anodes pole piece
Charge and discharge electric treatment is carried out, is first charged, setting charge cutoff voltage is 4.7V, then is discharged, discharge cut-off voltage 0.1V, charge and discharge
Current density is both configured to 10mA/g；After charge and discharge, charge and discharge power supply is cut off, anode pole piece and cathode pole piece pass through biography respectively
Dynamic device spreads out of electrolyte, and winds at winding；Finally respectively obtain the Li of pre-deoxidation1.18Mn0.492Ni0.164Co0.164O2
The SiOx cathode pole piece of anode pole piece and prelithiation.
By the Li of obtained pre-deoxidation1.18Mn0.492Ni0.164Co0.164O2Anode pole piece and commercial graphite cathode pole piece into
Row matching (cathode excessive 5%) is cut respectively, is weighed, vacuum outgas, fluid injection, sealing etc., being prepared
Li1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery.
The SiOx pole piece of obtained prelithiation is assembled into button cell together with Li piece, obtains SiOx/Li button cell.
The Li of preparation1.18Mn0.492Ni0.164Co0.164O2/ graphite full battery, first circle charge specific capacity are 273.56mAh/g,
First circle specific discharge capacity is 265.21mAh/g, efficiency for charge-discharge 96.95%.
The SiOx/Li button cell of preparation, first circle specific discharge capacity are 1546.94mAh/g, and first circle charge specific capacity is
1405.34mAh/g efficiency for charge-discharge 90.85%.
Embodiment 7
The Li that will be prepared1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and Si cathode pole piece according to Fig. 1 shown device at
Reason.The anode pole piece prepared is fed from positive plate entrance, is carried on transmission device A；The cathode pole piece prepared is thought highly of oneself
The charging of pole piece entrance, is carried on transmission device B；Anode pole piece and cathode pole piece pass through transmission device respectively and are sent into electrolyte
In (LiPF6 (1mol/L)/EC+DEC+EMC (1:1:1)), then stop transmission；Charge and discharge power supply is connected, to positive and negative anodes pole piece
Charge and discharge electric treatment is carried out, is first charged, setting charge cutoff voltage is 4.8V, then is discharged, discharge cut-off voltage 1V, charge and discharge electricity
Current density is both configured to 1mA/g；After charge and discharge, charge and discharge power supply is cut off, anode pole piece and cathode pole piece pass through transmission respectively
Device spreads out of electrolyte, and winds at winding；Finally respectively obtain the Li of pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Anode
The Si cathode pole piece of pole piece and prelithiation.
By the Li of obtained pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Anode pole piece and commercial graphite cathode pole piece carry out
Matching (cathode excessive 5%) is cut respectively, is weighed, vacuum outgas, fluid injection, sealing etc., being prepared
Li1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery.
The Si pole piece of obtained prelithiation is assembled into button cell together with Li piece, obtains Si/Li button cell.
The Li of preparation1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery, first circle charge specific capacity is 268.24mAh/g, first
Circle specific discharge capacity is 260.52mAh/g, efficiency for charge-discharge 97.12%.
The Si/Li button cell of preparation, first circle specific discharge capacity are 1489.29mAh/g, and first circle charge specific capacity is
1396.09mAh/g efficiency for charge-discharge 93.70%.
Comparative example
The Li that will be handled without pre-deoxidation1.2Mn0.54Ni0.13Co0.13O2Anode pole piece is directly matched with commercial graphite cathode
(cathode excessive 5%) prepares full battery, is cut, is weighed respectively, vacuum outgas, fluid injection, sealing etc., obtained
Li1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery.The SiOx-C pole piece handled without prelithiation is assembled into together with Li piece
Button cell obtains SiOx-C/Li button cell.
The Li of preparation1.2Mn0.54Ni0.13Co0.13O2/ graphite full battery, C-V(specific capacity-voltage) curve such as Fig. 4 institute
Show, first circle charge specific capacity is 354.52mAh/g, and first circle specific discharge capacity is 268.67mAh/g, and efficiency for charge-discharge is
75.78%。
The SiOx-C/Li button cell of preparation, C-V(specific capacity-voltage) curve as shown in figure 5, first circle discharge specific volume
Amount is 1680.70mAh/g, and first circle charge specific capacity is 1291.42mAh/g, efficiency for charge-discharge 76.84%.
Comparative example 1 and comparative example, the positive electrode after pre-deoxidation, in the feelings for guaranteeing its first circle discharge capacity
Under condition, first circle efficiency for charge-discharge is significantly improved.Its cycle performance is as shown in Figure 6, it is found that the anode without pre-deoxidation processing
It is 70.35% that material, which is assembled into capacity retention ratio after full battery recycles 100 times, and passes through the positive electrode assembling of pre-deoxidation processing
Capacity retention ratio is 93.13% after helping circulating battery 100 times, and the service life significantly improves.Negative electrode material after prelithiation, it is first
Circle efficiency for charge-discharge is also improved significantly.
Claims (10)
1. a kind of realize simultaneously to positive electrode pre-deoxidation, to the device of negative electrode material prelithiation, it is characterised in that: described
Device includes working bin, the electrolyte in working bin, protective cover, transmission device and power supply unit；The protective cover is divided into guarantor
Shield A and protective cover B, and being connected to respectively with working bin left and right ends, sets that there are two doors, i.e. positive plate entrance on protective cover A
With negative electrode tab entrance, set that there are two doors, i.e. positive plate outlet and negative electrode tab outlet on protective cover B；The transmission device point
It include that positive plate unreels, positive plate is wound and several positive plate driving cogs for transmission device A and transmission device B, transmission device A
Wheel, transmission device B include that negative electrode tab unreels, negative electrode tab is wound and several negative electrode tab transmission gears, transmission device A and transmission device
B can be such that positive/negative plate is driven between protective cover and working bin respectively；The power supply unit include charge and discharge power supply, conducting wire and
Power supply gear；The power supply gear be divided into power supply gear A and power supply gear B, and by conducting wire respectively with charge and discharge two poles
It is connected.
2. one kind according to claim 1 is realized simultaneously to positive electrode pre-deoxidation, to the dress of negative electrode material prelithiation
It sets, it is characterised in that: the electrolyte is Li salt/organic solvent electrolyte.
3. one kind according to claim 1 is realized simultaneously to positive electrode pre-deoxidation, to the dress of negative electrode material prelithiation
It sets, it is characterised in that: different voltage and electric current can be arranged in the charge and discharge power supply according to demand.
4. one kind according to claim 1 is realized simultaneously to positive electrode pre-deoxidation, to the dress of negative electrode material prelithiation
It sets, it is characterised in that: the power supply gear A and power supply gear B is in contact with anode pole piece and cathode pole piece respectively, and not
Influence the normal work of transmission device.
5. a kind of realized simultaneously using device as described in claim 1 to positive electrode pre-deoxidation, to the pre- lithium of negative electrode material
The method of change, which comprises the following steps:
(1) positive electrode sized mixing, be coated with, prepare anode pole piece, and be wound into a roll；Negative electrode material is sized mixing, is applied
Cloth prepares cathode pole piece, and is wound into a roll；
(2) coiled anode pole piece is fed from positive plate entrance, is carried on transmission device A；Certainly by coiled cathode pole piece
The charging of negative electrode tab entrance, is carried on transmission device B；
(3) start transmission device A and transmission device B, positive plate volume and negative electrode tab volume unreel respectively, positive and negative electrode pole piece transmitted
Enter in electrolyte, stops transmission；
(4) charge and discharge power supply is connected, charge and discharge electric treatment is carried out, after charge and discharge, disconnects charge and discharge power supply；
(5) transmission device A and transmission device B continue to be driven, and transmission distance is respectively LAAnd LB, then stop transmission, repeat step
(4)；
(6) charge and discharge treated anode pole piece and cathode pole piece are wound at positive plate winding and negative electrode tab winding respectively；
(7) the positive/negative plate volume after winding respectively obtains pre-deoxidation respectively from positive plate outlet and negative electrode tab outlet outflow
The cathode pole piece of anode pole piece and prelithiation.
6. one kind according to claim 5 is realized simultaneously to positive electrode pre-deoxidation, to the side of negative electrode material prelithiation
Method, it is characterised in that: the positive electrode is lithium-rich oxide anode material.
7. one kind according to claim 5 is realized simultaneously to positive electrode pre-deoxidation, to the side of negative electrode material prelithiation
Method, it is characterised in that: the negative electrode material includes Si, SiOx, Si-C compound or SiOx-C compound.
8. one kind according to claim 5 is realized simultaneously to positive electrode pre-deoxidation, to the side of negative electrode material prelithiation
Method, it is characterised in that: the charge and discharge electric treatment, which refers to, first charges to positive and negative anodes pole piece, then discharges, charge cutoff voltage 4.6
~ 4.8V, discharge cut-off voltage are 0.1 ~ 2V, and charging and discharging currents density is 1mA/g ~ 1000mA/g.
9. one kind according to claim 5 is realized simultaneously to positive electrode pre-deoxidation, to the side of negative electrode material prelithiation
Method, it is characterised in that: the transmission distance LARefer to the length for immersing the anode pole piece of anolyte portion；The transmission away from
From LBRefer to the length for immersing the cathode pole piece of anolyte portion.
10. one kind according to claim 9 is realized simultaneously to positive electrode pre-deoxidation, to the side of negative electrode material prelithiation
Method, it is characterised in that: the anode pole piece and cathode pole piece of the immersion anolyte portion can manufacture song in electrolyte
Folding, circuitous.
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