CN110518189B - Device and method for simultaneously realizing pre-deoxidation of anode material and pre-lithiation of cathode material - Google Patents
Device and method for simultaneously realizing pre-deoxidation of anode material and pre-lithiation of cathode material Download PDFInfo
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Abstract
A device and a method for simultaneously realizing pre-deoxidation of a positive electrode material and pre-lithiation of a negative electrode material belong to the field of lithium ion batteries. According to the invention, the lithium-rich layered oxide anode material is matched with the silicon cathode material to carry out charging and discharging treatment, and redundant lithium in the lithium-rich layered oxide anode material is used for pre-lithiation of the silicon cathode material, so that resource recycling is realized. The method has simple process, can simultaneously realize pre-deoxidation of the anode material and pre-lithium of the cathode material, has low cost and can realize large-scale production.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and particularly relates to a device and a method for simultaneously realizing pre-deoxidation of a positive electrode material and pre-lithiation of a negative electrode material.
Background
At present, with the gradual prohibition of selling fuel vehicles, lithium ion batteries already occupy the mainstream market of electric automobiles, and the rapid development of electric automobiles puts higher and higher requirements on the energy density of the lithium ion batteries. The traditional anode and cathode materials can not meet the market of electric automobiles developing at a high speed gradually, and the development of novel anode and cathode materials of lithium ion batteries is urgently needed. The lithium-rich layered oxide cathode material is gradually paid attention by researchers due to the advantages of high specific discharge capacity (> 250 mAh/g), high safety, low cost and the like, and is one of the potential next-generation lithium ion battery cathode materials. Meanwhile, the silicon negative electrode material has become a subject of controversial research and layout in the field of lithium ion battery negative electrode materials due to the high specific discharge capacity (to 2000mAh/g, which is far larger than that of the current commercial negative electrode material (400 to 600 mAh/g)).
However, lithium-rich layered oxide cathode materials have limited their commercial applications due to problems such as poor rate performance, low cycle life, voltage decay, etc. In particular, the first cycle of the lithium-rich layered oxide positive electrode material has low charging and discharging efficiency, and a large amount of lithium cannot reversibly return to the positive electrode, i.e., the first cycle can cause a large amount of active lithium loss, and the lithium-rich layered oxide positive electrode material cannot be applied subsequently. This portion of lithium continues to remain in the negative electrode material, which also results in a waste of negative electrode material matching it and reduces the energy density of the full cell. In addition, during the first cycle formation of the lithium-rich layered oxide material, a part of oxygen is separated out, which causes corrosion to the electrolyte, and further reduces the cycle life of the lithium-rich layered oxide material. Therefore, how to reduce or avoid the waste of lithium resources in the first cycle of the lithium-rich layered oxide material and how to avoid the corrosion of the electrolyte by the oxygen evolved in the first cycle are problems that must be solved for commercial application.
On the other hand, the problems of low first charge-discharge efficiency, poor cycle stability and the like of the silicon-based negative electrode material still cannot be solved. The silicon negative electrode material has abundant lithium insertion sites, but after lithium ions are inserted, a part of lithium cannot be reversibly extracted, but is retained in the negative electrode material to become dead lithium and lose activity. The first charge and discharge efficiency of the material is low, a large amount of lithium resources are wasted, and the energy density of the whole full battery is indirectly reduced. Therefore, in order to increase the energy density of the full cell, it is necessary to pre-lithiate the negative electrode material to improve the first effect thereof.
The pre-lithiation process is an effective method for solving the problems of low first-effect of electrode materials and improving the energy density of the full battery. During the formation of the lithium ion battery, the capacity loss of the lithium ion battery can be caused by the consumption of Li due to the formation of an SEI film or the inactivation of active Li due to the reason of the electrode material. The pre-lithiation of the electrode material can supplement the irreversible capacity loss of the battery in the first cycle process, and is beneficial to the improvement of the cycle life and the energy density of the battery.
At present, the method for prelithiation mainly comprises the step of prelithiation of lithium metal (such as lithium powder and lithium sheets) on a negative electrode, the method not only wastes lithium resources, but also has harsh requirements on working environment, large investment and is easier to cause potential safety hazard, and a novel prelithiation method which is safe, economical and easy to operate is urgently needed to be provided.
In the related technology, different researchers use different methods, but the problems of high production cost, harsh working environment, insignificant effect and the like exist. Therefore, in the current scientific research and production, a device and a method which can simultaneously realize the pre-deoxidation of the positive electrode material and the pre-lithiation of the negative electrode material, have the advantages of resource saving, simple process, low production cost and obvious performance effect and can be produced in a large scale are needed.
Disclosure of Invention
In order to solve the problems of low first-loop charge-discharge efficiency, poor cycle performance and the like of a lithium-rich layered oxide positive electrode material and a silicon negative electrode material, the invention provides a device and a method for simultaneously realizing pre-de-oxidation of the positive electrode material and pre-lithiation of the negative electrode material.
The device and the method can simultaneously realize the pre-deoxidation of the anode material and the pre-lithiation of the cathode material.
The anode material is a lithium-rich layered oxide anode material, and the cathode material comprises Si, SiOx, Si-C compound and SiOx-C compound.
The device of the invention is shown in figure 1: the device comprises a working bin, electrolyte in the working bin, a protective cover, a transmission device and a power supply device; the protective cover is divided into a protective cover A and a protective cover B and is respectively communicated with the left end and the right end of the working bin, two bin gates, namely a positive plate inlet and a negative plate inlet, are arranged on the protective cover A, and two bin gates, namely a positive plate outlet and a negative plate outlet, are arranged on the protective cover B; the transmission device is divided into a transmission device A and a transmission device B, the transmission device A comprises a positive plate unreeling device, a positive plate reeling device and a plurality of positive plate transmission gears, the transmission device B comprises a negative plate unreeling device, a negative plate reeling device and a plurality of negative plate transmission gears, and the transmission device A and the transmission device B can respectively enable the positive plate and the negative plate to be transmitted between the protective cover and the working bin; the power supply device comprises a charge and discharge source, a lead and a power supply gear; the power supply gear is divided into a power supply gear A and a power supply gear B, and is respectively connected with two poles of the charge and discharge source through leads. The electrolyte is Li salt/organic solvent electrolyte. The charging and discharging source can set different voltages and currents according to requirements. The power supply gear A and the power supply gear B are respectively contacted with the positive pole piece and the negative pole piece, and the normal work of the transmission device is not influenced.
The method comprises the following specific working steps:
(1) preparing a positive pole piece by carrying out size mixing, coating and the like on the positive pole material, and winding the positive pole piece into a coil; preparing a negative pole piece by mixing and coating the negative pole material, and winding the negative pole piece into a coil;
(2) feeding the coiled positive pole piece from the positive pole piece inlet, and loading the coiled positive pole piece on a transmission device A; feeding the coiled negative pole piece from the negative pole piece inlet, and loading the coiled negative pole piece on a transmission device B;
(3) starting the transmission device A and the transmission device B, respectively unwinding the positive pole piece roll and the negative pole piece roll, transmitting the positive pole piece and the negative pole piece into the electrolyte, and stopping transmission;
(4) switching on a charge and discharge source, carrying out charge and discharge treatment, and switching off the charge and discharge source after charge and discharge are finished;
(5) the transmission device A and the transmission device B continue to transmit, and the transmission distances are L respectivelyAAnd LBAnd stopping transmission. Repeating the step 4;
(6) the positive pole piece and the negative pole piece after the charging and discharging treatment are respectively wound at a positive pole piece winding position and a negative pole piece winding position;
(7) and the wound positive and negative pole piece rolls are respectively transmitted out from the positive pole piece outlet and the negative pole piece outlet to respectively obtain a pre-deoxidized positive pole piece and a pre-lithiated negative pole piece.
In the working step (4), the charge and discharge treatment refers to charging and then discharging the positive and negative electrode plates, the charge cut-off voltage is 4.6-4.8V, the discharge cut-off voltage is 0.1-2V, and the charge and discharge current density is 1 mA/g-1000 mA/g.
In the working step (5), the transmission distance LARefers to the positive electrode immersed in the electrolyteThe length of the sheet; the transmission distance LBThe length of the negative pole piece immersed in the electrolyte is referred to; the length of the positive pole piece and the length of the negative pole piece of the part immersed in the electrolyte can be increased by manufacturing a zigzag and circuitous line in the electrolyte, so that the efficiency is improved.
The invention has the following beneficial effects:
(1) in the first cycle of charge and discharge of the lithium-rich layered oxide cathode material, part of lithium cannot return to the cathode due to the material, and still stays in the cathode material. In the first cycle of charge and discharge of the silicon-based negative electrode material, part of active lithium can be retained in the negative electrode material due to the properties of the material, and the active lithium is inactivated. The lithium-rich layered oxide anode material is matched with the silicon cathode material to carry out charge and discharge treatment, and redundant lithium in the lithium-rich layered oxide anode material is used for pre-lithiation of the silicon cathode material, so that resource recycling is realized;
(2) after the lithium-rich layered oxide anode material is subjected to pre-deoxidation treatment, the corrosion of separated oxygen to the electrolyte is avoided, so that the cycle life of the lithium-rich layered oxide anode material is greatly prolonged;
(3) after the pre-lithiation treatment is carried out on the silicon negative electrode material, the energy density of the full battery can be greatly improved;
(4) the method has simple process, can simultaneously realize pre-deoxidation of the anode material and pre-lithium of the cathode material, has low cost and is completed in one step;
(5) the positive and negative pole pieces treated by the process have the advantages of obvious and reliable performance improvement, environmental friendliness, uniform product quality, good repeatability and large-scale production.
Drawings
FIG. 1: the device of the invention. In the figure: 1, a working bin; 2-an electrolyte; 3-protective cover a; 4-protective cover B; 5-transmission device A; 6-transmission device B; 7-a power supply device; 31-positive plate inlet; 32-negative plate entrance; 41-outlet of positive plate; 42-cathode plate outlet; 51, unwinding a positive plate; 52-positive pole piece transmission gear; 53, winding the positive plate; 61-unwinding the negative plate; 62-negative pole piece transmission gear; 63-rolling the negative plate; 71-charge and discharge source; 72-supply gear B; 73-power supply gear a; 74-wire.
FIG. 2: li in example 1 of the present invention1.2Mn0.54Ni0.13Co0.13O2C-V (specific capacity-voltage) curve of graphite full cell.
FIG. 3: the C-V (specific capacity-voltage) curve of the SiOx-C/Li button cell of example 1 of the invention.
FIG. 4: comparative example of the present invention Li1.2Mn0.54Ni0.13Co0.13O2C-V (specific capacity-voltage) curve of graphite full cell.
FIG. 5: the C-V (specific capacity-voltage) curve of the SiOx-C/Li button cell of the comparative example of the invention.
FIG. 6: comparative example of the invention and Li in example 11.2Mn0.54Ni0.13Co0.13O2The cycle performance of the graphite full cell at 0.5C rate.
Detailed description of the preferred embodiments
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the principle and scope of the technical solution of the present invention, and shall be covered within the protection scope of the present invention.
Example 1
Mixing Li1.2Mn0.54Ni0.13Co0.13O2Preparing a positive pole piece by carrying out size mixing, coating and the like on the positive pole material, and winding the positive pole piece into a coil; and (3) carrying out size mixing, coating and the like on the SiOx-C negative electrode material to prepare a negative electrode piece, and winding the negative electrode piece into a coil. Prepared Li1.2Mn0.54Ni0.13Co0.13O2The positive electrode sheet and the SiOx-C negative electrode sheet were processed in accordance with the apparatus shown in FIG. 1. Feeding the prepared positive pole piece from a positive pole piece inlet, and bearing the positive pole piece on a transmission device A; feeding the prepared negative pole piece from a negative pole piece inlet, and bearing the negative pole piece on a transmission device B; the positive pole piece and the negative pole piece are respectively fed into the electrolyte through a transmission device(LiPF 6(1mol/L)/EC + DEC (1: 1)) and then stopping the transmission; switching on a charge and discharge source, carrying out charge and discharge treatment on the positive and negative pole pieces, firstly charging, setting the charge cut-off voltage to be 4.7V, and then discharging, wherein the discharge cut-off voltage is 0.1V, and the charge and discharge current density is set to be 10 mA/g; after charging and discharging are finished, a charging and discharging power source is cut off, and the positive pole piece and the negative pole piece are respectively transmitted out of the electrolyte through the transmission device and are wound at a winding position; finally respectively obtaining pre-deoxidized Li1.2Mn0.54Ni0.13Co0.13O2Positive pole piece and pre-lithiated SiOx-C negative pole piece.
The pre-de-oxidized Li obtained1.2Mn0.54Ni0.13Co0.13O2Matching the positive pole piece with a commercial graphite negative pole piece (5% of excessive negative pole), respectively cutting, weighing, vacuum degassing, injecting liquid, sealing and the like to prepare the Li1.2Mn0.54Ni0.13Co0.13O2A graphite full cell.
And assembling the obtained pre-lithiated SiOx-C pole piece and the Li piece together to form the button cell to obtain the SiOx-C/Li button cell.
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The C-V (specific capacity-voltage) curve of the graphite full battery is shown in figure 2, the charging specific capacity of the first circle is 275.65mAh/g, the discharging specific capacity of the first circle is 267.99mAh/g, and the charging and discharging efficiency is 97.22%.
The C-V (specific capacity-voltage) curve of the prepared SiOx-C/Li button cell is shown in figure 3, the first-circle specific discharge capacity is 1350.22mAh/g, the first-circle specific charge capacity is 1310.17mAh/g, and the charge-discharge efficiency is 97.03%.
Example 2
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The positive electrode sheet and the SiOx-C negative electrode sheet were processed in accordance with the apparatus shown in FIG. 1. Feeding the prepared positive pole piece from a positive pole piece inlet, and bearing the positive pole piece on a transmission device A; feeding the prepared negative pole piece from a negative pole piece inlet, and bearing the negative pole piece on a transmission device B; the positive pole piece and the negative pole piece respectively pass throughThe transmission device is fed into the electrolyte (LiPF 6(1mol/L)/EC + DEC (1: 1)) and then the transmission is stopped; switching on a charge and discharge source, carrying out charge and discharge treatment on the positive and negative pole pieces, firstly charging, setting the charge cut-off voltage to be 4.6V, and then discharging, wherein the discharge cut-off voltage is 0.1V, and the charge and discharge current density is set to be 1000 mA/g; after charging and discharging are finished, a charging and discharging power source is cut off, and the positive pole piece and the negative pole piece are respectively transmitted out of the electrolyte through the transmission device and are wound at a winding position; finally respectively obtaining pre-deoxidized Li1.2Mn0.54Ni0.13Co0.13O2Positive pole piece and pre-lithiated SiOx-C negative pole piece.
The pre-de-oxidized Li obtained1.2Mn0.54Ni0.13Co0.13O2Matching the positive pole piece with a commercial graphite negative pole piece (5% of excessive negative pole), respectively cutting, weighing, vacuum degassing, injecting liquid, sealing and the like to prepare the Li1.2Mn0.54Ni0.13Co0.13O2A graphite full cell.
And assembling the obtained pre-lithiated SiOx-C pole piece and the Li piece together to form the button cell to obtain the SiOx-C/Li button cell.
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The first circle of the graphite full battery has the specific charge capacity of 263.82mAh/g, the first circle of the graphite full battery has the specific discharge capacity of 245.05mAh/g, and the charge-discharge efficiency is 92.88%.
The first circle of the prepared SiOx-C/Li button cell has the specific discharge capacity of 1316.91mAh/g, the first circle of the prepared SiOx-C/Li button cell has the specific charge capacity of 1245.59mAh/g, and the charge-discharge efficiency of 94.58%.
Example 3
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The positive electrode sheet and the SiOx-C negative electrode sheet were processed in accordance with the apparatus shown in FIG. 1. Feeding the prepared positive pole piece from a positive pole piece inlet, and bearing the positive pole piece on a transmission device A; feeding the prepared negative pole piece from a negative pole piece inlet, and bearing the negative pole piece on a transmission device B; the positive pole piece and the negative pole piece are respectively sent into electrolyte (LiPF 6(1mol/L)/EC + DEC (1: 1)) through a transmission device and then stoppedStopping transmission; switching on a charge and discharge source, carrying out charge and discharge treatment on the positive and negative pole pieces, firstly charging, setting the charge cut-off voltage to be 4.8V, and then discharging, setting the discharge cut-off voltage to be 2V, and setting the charge and discharge current density to be 1 mA/g; after charging and discharging are finished, a charging and discharging power source is cut off, and the positive pole piece and the negative pole piece are respectively transmitted out of the electrolyte through the transmission device and are wound at a winding position; finally respectively obtaining pre-deoxidized Li1.2Mn0.54Ni0.13Co0.13O2Positive pole piece and pre-lithiated SiOx-C negative pole piece.
The pre-de-oxidized Li obtained1.2Mn0.54Ni0.13Co0.13O2Matching the positive pole piece with a commercial graphite negative pole piece (5% of excessive negative pole), respectively cutting, weighing, vacuum degassing, injecting liquid, sealing and the like to prepare the Li1.2Mn0.54Ni0.13Co0.13O2A graphite full cell.
And assembling the obtained pre-lithiated SiOx-C pole piece and the Li piece together to form the button cell to obtain the SiOx-C/Li button cell.
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The first circle of the graphite full battery has the charge specific capacity of 261.44mAh/g, the first circle of the graphite full battery has the discharge specific capacity of 252.96mAh/g, and the charge-discharge efficiency is 96.76%.
The first circle of the prepared SiOx-C/Li button cell has the specific discharge capacity of 1329.11mAh/g, the first circle of the prepared SiOx-C/Li button cell has the specific charge capacity of 1216.36mAh/g, and the charge-discharge efficiency of 91.51%.
Example 4
Prepared Li1.18Mn0.492Ni0.164Co0.164O2The positive electrode sheet and the SiOx-C negative electrode sheet were processed in accordance with the apparatus shown in FIG. 1. Feeding the prepared positive pole piece from a positive pole piece inlet, and bearing the positive pole piece on a transmission device A; feeding the prepared negative pole piece from a negative pole piece inlet, and bearing the negative pole piece on a transmission device B; the positive pole piece and the negative pole piece are respectively sent into electrolyte (LiPF 6(1mol/L)/EC + DMC (1: 1)) through a transmission device, and then the transmission is stopped; a charge and discharge source is switched on, the charge and discharge treatment is carried out on the positive and negative pole pieces,firstly, charging, setting the charge cut-off voltage to be 4.7V, and then discharging, wherein the discharge cut-off voltage is 0.1V, and the charge-discharge current density is set to be 10 mA/g; after charging and discharging are finished, a charging and discharging power source is cut off, and the positive pole piece and the negative pole piece are respectively transmitted out of the electrolyte through the transmission device and are wound at a winding position; finally respectively obtaining pre-deoxidized Li1.18Mn0.492Ni0.164Co0.164O2Positive pole piece and pre-lithiated SiOx-C negative pole piece.
The pre-de-oxidized Li obtained1.18Mn0.492Ni0.164Co0.164O2Matching the positive pole piece with a commercial graphite negative pole piece (5% of excessive negative pole), respectively cutting, weighing, vacuum degassing, injecting liquid, sealing and the like to prepare the Li1.18Mn0.492Ni0.164Co0.164O2A graphite full cell.
And assembling the obtained pre-lithiated SiOx-C pole piece and the Li piece together to form the button cell to obtain the SiOx-C/Li button cell.
Prepared Li1.18Mn0.492Ni0.164Co0.164O2The first circle of the graphite full battery has the specific charge capacity of 273.90mAh/g, the first circle of the graphite full battery has the specific discharge capacity of 265.07mAh/g, and the charge-discharge efficiency is 96.78%.
The first circle of the prepared SiOx-C/Li button cell has the specific discharge capacity of 1346.52mAh/g, the first circle of the prepared SiOx-C/Li button cell has the specific charge capacity of 1305.23mAh/g, and the charge-discharge efficiency is 96.93%.
Example 5
Prepared Li1.18Mn0.492Ni0.164Co0.164O2The positive electrode piece and the Si-C negative electrode piece were processed according to the apparatus shown in FIG. 1. Feeding the prepared positive pole piece from a positive pole piece inlet, and bearing the positive pole piece on a transmission device A; feeding the prepared negative pole piece from a negative pole piece inlet, and bearing the negative pole piece on a transmission device B; the positive pole piece and the negative pole piece are respectively sent into electrolyte (LiPF 6(1mol/L)/EC + DMC (1: 1)) through a transmission device, and then the transmission is stopped; switching on a charge-discharge source, performing charge-discharge treatment on the positive and negative electrode plates, charging, setting the charge cut-off voltage to be 4.8V, discharging,the discharge cut-off voltage is 1V, and the charge and discharge current density is set to be 1 mA/g; after charging and discharging are finished, a charging and discharging power source is cut off, and the positive pole piece and the negative pole piece are respectively transmitted out of the electrolyte through the transmission device and are wound at a winding position; finally respectively obtaining pre-deoxidized Li1.18Mn0.492Ni0.164Co0.164O2Positive pole piece and pre-lithiated SiOx-C negative pole piece.
The pre-de-oxidized Li obtained1.18Mn0.492Ni0.164Co0.164O2Matching the positive pole piece with a commercial graphite negative pole piece (5% of excessive negative pole), respectively cutting, weighing, vacuum degassing, injecting liquid, sealing and the like to prepare the Li1.18Mn0.492Ni0.164Co0.164O2A graphite full cell.
And assembling the obtained pre-lithiated Si-C pole piece and the Li piece together to form the button cell to obtain the Si-C/Li button cell.
Prepared Li1.18Mn0.492Ni0.164Co0.164O2The first circle of the graphite full battery has the specific charge capacity of 271.38mAh/g, the first circle of the graphite full battery has the specific discharge capacity of 262.03mAh/g, and the charge-discharge efficiency is 96.55%.
The first circle of the prepared Si-C/Li button cell has the specific discharge capacity of 1389.18mAh/g, the first circle of the prepared Si-C/Li button cell has the specific charge capacity of 1326.60mAh/g, and the charge-discharge efficiency is 95.50%.
Example 6
Prepared Li1.18Mn0.492Ni0.164Co0.164O2The positive electrode sheet and the SiOx negative electrode sheet were processed in accordance with the apparatus shown in fig. 1. Feeding the prepared positive pole piece from a positive pole piece inlet, and bearing the positive pole piece on a transmission device A; feeding the prepared negative pole piece from a negative pole piece inlet, and bearing the negative pole piece on a transmission device B; the positive pole piece and the negative pole piece are respectively sent into electrolyte (LiPF 6(1mol/L)/EC + DEC + EMC (1:1: 1)) through a transmission device, and then the transmission is stopped; switching on charge and discharge source, performing charge and discharge treatment on the positive and negative electrode plates, charging, setting charge cut-off voltage to 4.7V, and discharging, setting discharge cut-off voltage to 0.1V, and setting charge and discharge current density to10 mA/g; after charging and discharging are finished, a charging and discharging power source is cut off, and the positive pole piece and the negative pole piece are respectively transmitted out of the electrolyte through the transmission device and are wound at a winding position; finally respectively obtaining pre-deoxidized Li1.18Mn0.492Ni0.164Co0.164O2Positive pole piece and the negative pole piece of SiOx of prelithiation.
The pre-de-oxidized Li obtained1.18Mn0.492Ni0.164Co0.164O2Matching the positive pole piece with a commercial graphite negative pole piece (5% of excessive negative pole), respectively cutting, weighing, vacuum degassing, injecting liquid, sealing and the like to prepare the Li1.2Mn0.54Ni0.13Co0.13O2A graphite full cell.
And assembling the obtained pre-lithiated SiOx pole piece and the Li piece together to form the button cell to obtain the SiOx/Li button cell.
Prepared Li1.18Mn0.492Ni0.164Co0.164O2The first circle of the graphite full battery has the specific charge capacity of 273.56mAh/g, the first circle of the graphite full battery has the specific discharge capacity of 265.21mAh/g, and the charge-discharge efficiency is 96.95%.
The first circle of the prepared SiOx/Li button cell has the discharge specific capacity of 1546.94mAh/g, the first circle of the prepared SiOx/Li button cell has the charge specific capacity of 1405.34mAh/g, and the charge-discharge efficiency is 90.85%.
Example 7
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The positive and Si negative electrode pieces were processed according to the apparatus shown in fig. 1. Feeding the prepared positive pole piece from a positive pole piece inlet, and bearing the positive pole piece on a transmission device A; feeding the prepared negative pole piece from a negative pole piece inlet, and bearing the negative pole piece on a transmission device B; the positive pole piece and the negative pole piece are respectively sent into electrolyte (LiPF 6(1mol/L)/EC + DEC + EMC (1:1: 1)) through a transmission device, and then the transmission is stopped; switching on a charge and discharge source, carrying out charge and discharge treatment on the positive and negative pole pieces, firstly charging, setting the charge cut-off voltage to be 4.8V, and then discharging, setting the discharge cut-off voltage to be 1V, and setting the charge and discharge current density to be 1 mA/g; after the charge and discharge are finished, the charge and discharge source, the positive pole piece and the negative pole are cut offThe pole pieces are respectively transmitted out of the electrolyte through a transmission device and are wound at a winding position; finally respectively obtaining pre-deoxidized Li1.2Mn0.54Ni0.13Co0.13O2Positive pole piece and pre-lithiated Si negative pole piece.
The pre-de-oxidized Li obtained1.2Mn0.54Ni0.13Co0.13O2Matching the positive pole piece with a commercial graphite negative pole piece (5% of excessive negative pole), respectively cutting, weighing, vacuum degassing, injecting liquid, sealing and the like to prepare the Li1.2Mn0.54Ni0.13Co0.13O2A graphite full cell.
And assembling the obtained pre-lithiated Si pole piece and the Li piece together to form the button cell to obtain the Si/Li button cell.
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The first circle of the graphite full battery has the specific charge capacity of 268.24mAh/g, the first circle of the graphite full battery has the specific discharge capacity of 260.52mAh/g, and the charge-discharge efficiency is 97.12%.
The first circle of the prepared Si/Li button cell has the discharge specific capacity of 1489.29mAh/g, the first circle of the prepared Si/Li button cell has the charge specific capacity of 1396.09mAh/g, and the charge-discharge efficiency is 93.70%.
Comparative example
Subjecting Li without pre-deoxidation treatment1.2Mn0.54Ni0.13Co0.13O2The positive pole piece is directly matched with a commercial graphite negative pole (the negative pole is excessive by 5 percent), a full battery is prepared, and cutting, weighing, vacuum degassing, liquid injection, sealing and the like are respectively carried out to obtain Li1.2Mn0.54Ni0.13Co0.13O2A graphite full cell. And assembling the SiOx-C pole piece which is not subjected to pre-lithiation treatment and the Li piece together to form the button cell to obtain the SiOx-C/Li button cell.
Prepared Li1.2Mn0.54Ni0.13Co0.13O2The C-V (specific capacity-voltage) curve of the graphite full battery is shown in figure 4, the charging specific capacity of the first circle is 354.52mAh/g, the discharging specific capacity of the first circle is 268.67mAh/g, and the charging and discharging efficiency is 75.78%.
The C-V (specific capacity-voltage) curve of the prepared SiOx-C/Li button cell is shown in figure 5, the first-circle specific discharge capacity is 1680.70mAh/g, the first-circle specific charge capacity is 1291.42mAh/g, and the charge-discharge efficiency is 76.84%.
Comparing example 1 with the comparative example, the charge-discharge efficiency of the first cycle is obviously improved under the condition of ensuring the first cycle discharge capacity of the pre-deoxidized positive electrode material. As shown in fig. 6, the cycle performance of the positive electrode material is that the capacity retention rate is 70.35% after the positive electrode material is assembled into a full cell without pre-deoxidation treatment and the capacity retention rate is 93.13% after the positive electrode material is assembled into a full cell after 100 cycles, and the service life is obviously improved. The charge-discharge efficiency of the anode material after pre-lithiation in the first circle is also obviously improved.
Claims (4)
1. A method for simultaneously realizing pre-de-oxidation of a positive electrode material and pre-lithiation of a negative electrode material is characterized in that the positive electrode material and the negative electrode material are matched for charge and discharge treatment, redundant lithium in the positive electrode material is used for pre-lithiation of the negative electrode material, and meanwhile, the positive electrode material realizes self pre-de-oxidation; the anode material is a lithium-rich layered oxide anode material, and the cathode material comprises Si, SiOx, a Si-C compound or a SiOx-C compound; the device corresponding to the method comprises a working bin, Li salt/organic solvent electrolyte in the working bin, a protective cover, a transmission device and a power supply device; the protective cover is divided into a protective cover A and a protective cover B and is respectively communicated with the left end and the right end of the working bin, two bin gates, namely a positive plate inlet and a negative plate inlet, are arranged on the protective cover A, and two bin gates, namely a positive plate outlet and a negative plate outlet, are arranged on the protective cover B; the transmission device is divided into a transmission device A and a transmission device B, the transmission device A comprises a positive plate unreeling device, a positive plate reeling device and a plurality of positive plate transmission gears, the transmission device B comprises a negative plate unreeling device, a negative plate reeling device and a plurality of negative plate transmission gears, and the transmission device A and the transmission device B can respectively enable the positive plate and the negative plate to be transmitted between the protective cover and the working bin; the power supply device comprises a charge and discharge source, a lead and a power supply gear; the power supply gear is divided into a power supply gear A and a power supply gear B, and is respectively connected with two poles of the charge and discharge source through leads, and the power supply gear A and the power supply gear B are respectively contacted with the positive pole piece and the negative pole piece without influencing the normal work of the transmission device; the method comprises the following specific steps:
(1) mixing and coating the positive electrode material to prepare a positive electrode piece, and winding the positive electrode piece into a coil; mixing and coating the negative electrode material to prepare a negative electrode plate, and winding the negative electrode plate into a coil;
(2) feeding the coiled positive pole piece from the positive pole piece inlet, and loading the coiled positive pole piece on a transmission device A; feeding the coiled negative pole piece from the negative pole piece inlet, and loading the coiled negative pole piece on a transmission device B;
(3) starting the transmission device A and the transmission device B, respectively unwinding the positive pole piece roll and the negative pole piece roll, transmitting the positive pole piece and the negative pole piece into the electrolyte, and stopping transmission;
(4) switching on a charge and discharge source, carrying out charge and discharge treatment, and switching off the charge and discharge source after charge and discharge are finished;
(5) the transmission device A and the transmission device B continue to transmit, and the transmission distances are L respectivelyAAnd LBThen stopping transmission, and repeating the step (4);
(6) the positive pole piece and the negative pole piece after the charging and discharging treatment are respectively wound at a positive pole piece winding position and a negative pole piece winding position;
(7) and the wound positive and negative pole piece rolls are respectively transmitted out from the positive pole piece outlet and the negative pole piece outlet to respectively obtain a pre-deoxidized positive pole piece and a pre-lithiated negative pole piece.
2. The method for simultaneously pre-de-oxidizing the anode material and pre-lithiating the cathode material according to claim 1, wherein the method comprises the following steps: the charge and discharge treatment is to charge and discharge the positive and negative electrode plates, wherein the charge cut-off voltage is 4.6-4.8V, the discharge cut-off voltage is 0.1-2V, and the charge and discharge current density is 1 mA/g-1000 mA/g.
3. The method for simultaneously pre-de-oxidizing the anode material and pre-lithiating the cathode material according to claim 1, wherein the method comprises the following steps:the transmission distance LAThe length of the positive pole piece immersed in the electrolyte is referred to; the transmission distance LBRefers to the length of the negative electrode sheet immersed in the electrolyte.
4. The method for simultaneously pre-de-oxidizing the anode material and pre-lithiating the cathode material according to claim 3, wherein the method comprises the following steps: the positive pole piece and the negative pole piece which are immersed in the electrolyte part are provided with a zigzag and circuitous circuit in the electrolyte.
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