Art
[1]Mutual citations and related applications
[2]This application claims the benefit of priority based on the July 10th issue of Korea Patent Application No. 10-2017-0087274 and No. 07 in 2018, 09 dated Korea Patent Application No. 10-2018-0079493 2017, and of the Korea Patent Application everything described in the literature are included as part of the specification.
[3]Art
[4]
The present invention relates to a regeneration method of a lithium secondary battery.
BACKGROUND
[5]
This secondary battery has been developed, unlike primary cells, rechargeable, and due also to the small size and large capacity much potential research in recent years. The demand for secondary batteries as an energy source has increased dramatically as the development of technology and demand for mobile devices increases.
[6]
This secondary battery according to the shape of the battery case, the nose is classified as type battery, a cylindrical battery, a prismatic battery, and a pouch-shaped battery. The electrode assembly mounted inside the battery case in a secondary battery is a power generation device capable of charge and discharge made of a stacked structure of electrodes and separators.
[7]
The electrode assembly is interposed a separator between the anode and the cathode of the active material is applied to a sheet-like (介 在) by winding the jelly roll (Jelly-roll) stacked one type, stacking a plurality of positive and negative electrodes in a membrane interposed state type by, and a take-up stack of unit cells stacked as separate film of the longer length / folding type can be roughly classified.
[8]
On the other hand, the conventional lithium secondary batteries is to use a repeated lithium ion is charged, and move to the cathode from the anode in accordance with a repeated process of lithium ions to be discharged is moved to the positive electrode from the negative electrode and the lithium source is out gradually, because of this the battery capacity was decreased degradation. At present, to play these degenerate lithium secondary batteries is becoming how to re-use have been studied.
Detailed Description of the Invention
SUMMARY
[9]
One aspect of the present invention to provide a regeneration method of a lithium secondary battery that can improve the life characteristics of the lithium secondary battery.
[10]
It is another aspect of the present invention is to provide a regeneration method of a lithium secondary battery capable of re-supply of the lithium ions to the positive electrode through the lithium electrode material supply without dismantling the secondary battery recovery capacity of a battery.
[11]
In addition, another aspect of the present invention is to provide a regeneration method of a lithium secondary battery that can increase the recovery capacity of a battery by fully discharging the negative electrode through the lithium electrode material supply without dismantling the secondary battery to the discharge limit.
[12]
And, another aspect of the present invention to provide a regeneration method of a lithium secondary battery that can adjust the balance between the positive and negative electrodes
Problem solving means
[13]
Regeneration method of a lithium secondary battery according to an embodiment of the present invention, the electrode and the membrane, including the positive and negative electrodes are mobilized alternately stacked electrode assembly and a secondary battery including a battery case portions are formed receiving for receiving the electrode assembly in the regeneration process, the lithium material supply electrode further provided in the secondary battery, by setting the anode as a counter electrode, and setting the lithium material supply electrode to the working (Working) electrode, the over the lithium material supply electrode via both the lithium material feed step of charging a lithium ion as the anode and the re-supplying step re-supplying the lithium ions into the positive electrode, setting the lithium material supply electrode as the counter electrode, and by setting the negative electrode as the working electrode, including cathode discharge step of fully discharging the cathode to the discharge limits, it is possible to restore the capacity of the secondary battery.
Effects of the Invention
[14]
In accordance with the present invention, lithium is re-supplied to the electrodes are further provided a secondary battery, it is possible without dismantling the secondary battery to re-supply of the lithium ions to the positive electrode through the lithium electrode material supply recovery capacity of a battery.
[15]
In addition, according to the invention, by fully discharging the secondary battery to a lithium electrode material supplied to the negative electrode to discharge limits through without dismantling it it is possible to increase the recovery capacity of a battery. I.e., from cathode to anode of lithium ion movement and during discharge, it becomes lithium ions remaining in the negative electrode, but not the full discharge achieved, lithium material supply electrode to the counter electrode and by setting the anode as the working electrode of lithium material supply at the cathode while moving the lithium ions into the negative electrode can be completely discharged to a discharge limit.
[16]
And, according to the present invention, by adjusting the balance between the positive and negative electrodes to control the discharge amount of the material supply amount and the negative electrode of the lithium ion to the positive electrode through the lithium electrode material supplied, can significantly recovery than the electrode capacitance.
Brief Description of the Drawings
[17]
1 is a perspective view showing a lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the invention.
[18]
Figure 2 is a front view showing a lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the invention.
[19]
Figure 3 is an exploded perspective view showing an electrode assembly and a lithium electrode material supplied from the lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the invention.
[20]
Figure 4 is a front perspective view showing a lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the present invention by way of example.
[21]
5 is a bottom perspective view showing the lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the present invention by way of example.
[22]
Figure 6 is a graph of the Differential voltage data used in the determination step in the regeneration of a lithium secondary battery according to an embodiment of the invention.
[23]
7 is a graph showing a resistance change of the lithium secondary battery regenerated to the regeneration method of a lithium secondary battery according to an embodiment of the invention.
Mode for the Invention
[24]
An object of the present invention, particular advantages, and novel features will become more apparent from the detailed description and the preferred embodiments below that in connection with the accompanying drawings. In addition as the reference numerals to components in the drawings herein, hanhaeseoneun to like elements even though shown in different drawings, even if should be noted that and to have the same number as possible. In addition, the present invention is not be implemented in many different forms and limited to the embodiments set forth herein. Then, in the following description, detailed description of the related art which may unnecessarily obscure the subject matter of the present invention will be omitted.
[25]
[26]
1 is a perspective view showing a lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the present invention, Figure 2 is a lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the present invention a front view, Figure 3 is an exploded perspective view showing an electrode assembly and a lithium electrode material supplied from the lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the invention.
[27]
Referring to Figure 1 to Figure 3, the regeneration method of a lithium secondary battery according to an embodiment of the present invention is a lithium material supply step of charging the lithium ion to the anode 121 via the lithium material supply electrode 130 and the lithium material a negative electrode 122 to limit a discharge through a feed electrode 130, including the cathode discharge step of complete discharge, recruit the capacity of the secondary battery 100. Further, the regeneration method of a lithium secondary battery according to an embodiment of the present invention determines the degradation degree of the discharge phase, and a positive electrode 121 and negative electrode 122 for discharging to the discharge electrodes 123, before the lithium material supply step a determination step, and re-establish the balance step to re-establish the balance (balance) of the electrode 123, which may further include.
[28]
[29]
4 is a front perspective view showing a lithium secondary battery to be applied to the regeneration method of a lithium secondary battery according to an embodiment of the present invention by way of example, Figure 5 is applied to a regeneration method of a lithium secondary battery according to an embodiment of the present invention a bottom perspective view showing the lithium secondary battery by way of example.
[30]
In the following, with reference to FIG. 1 to FIG. 6, one embodiment of the present invention will be described in more detail for the regeneration method of towing a lithium secondary battery.
[31]
A battery case 3, and referring to Figure 4, the secondary battery 100 to be applied to the regeneration method of an embodiment of a lithium secondary battery of the present invention is added acceptable for receiving the electrode assembly 120 and electrode assembly 120 is formed ( 110) a. At this time, an exemplary secondary battery 100 to be applied to the regeneration method of towing a lithium secondary battery of the present invention can be accommodated in the battery case (110) further includes an electrolytic solution and a lithium electrode material supply (130).
[32]
The electrode assembly 120 includes a battery element can be charged and discharged, the electrode 123 and the separator 124 are aggregated to form a laminated alternately. The electrode assembly 120 may include an electrode lead (125 126) electrically connected to the electrode 123. In this case, the electrode assembly 120 may further include an electrode tabs (127 128) is formed to project to the side that is electrically connected to the electrode leads (125 126) of the electrode 123.
[33]
Electrode 123 may be composed of the positive electrode 121 and negative electrode 122. In this case, the electrode assembly 120 may be formed of a positive electrode 121 / separator 124 / negative electrode 122 laminated in this shift.
[34]
Anode 121 is the cathode current collector (not shown) and positive electrode current collector include the entire positive electrode active material (not shown) applied to, and a negative electrode 122 is a negative electrode active material applied on the negative electrode current collector (not shown) and a negative electrode current collector It may include (not shown).
[35]
The positive electrode collector may be made of example, the foil (foil) of aluminum (Al) material, for example.
[36]
The positive electrode active material may be formed of lithium manganese oxide for example, lithium cobalt oxide, lithium nickel oxide, lithium iron phosphate, or the like, and mixtures comprising one compound or more species of them.
[37]
In addition, the positive electrode active material may be made of another example Hi Ni-based cathode material. Here, it may be made by including at least one of a Ni-based cathode material LiNiMnCoO Hi-based, or based LiNiCoAl LiMiMnCoAl system.
[38]
The anode current collector may be made of, for example, copper (Cu) or nickel (Ni) foil material (foil) made of a.
[39]
Negative electrode active material may be made of a synthetic material which comprises a graphite as an example.
[40]
In addition, the negative electrode active material may be made of another example of a lithium metal, lithium alloys, carbon, petroleum coke, activated carbon, graphite, silicon compound, tin compound, titanium compound or an alloy thereof.
[41]
Membrane 124 is electrically insulated through the insulating material consists of a positive electrode 121 and negative electrode 122. The Here, the separator 124 may be located on the outer surface of and between the anode 121 and the cathode 122, anode 121 and cathode 122. The At this time, the outermost side of the separation membrane 134 may be provided in the form of surrounding the electrode assembly 120 so as to be located between the lithium material supply electrode 130 and positive electrode 121 and negative electrode 122. The
[42]
Further, the separator 124 is, for example, be formed of a polyolefin-based resin film such as polyethylene, polypropylene having a non-porous.
[43]
Electrode leads (125 126) may include a positive electrode 121 and the electrically positive electrode lead 125 and the cathode 122 and the electrically negative electrode lead 126 is connected to connected.
[44]
Electrode tabs (127 128) is protruded to the side of the positive electrode tab 127 and negative electrode 122 that protrudes to the side of the anode 121 connected to the anode 121 and the cathode lead 125. The negative lead to the negative electrode 122 It may comprise a 126 and the negative electrode tab 126 electrically connected.
[45]
Electrolyte solution, for example, may be formed of a non-aqueous electrolyte and a lithium salt as a lithium-containing non-aqueous liquid electrolyte.
[46]
Here, the non-aqueous electrolyte is, for example, N- methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma- butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy Franc (franc), 2- methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxy methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate the derivatives, tetrahydrofuran derivatives, aprotic organic solvent such as ether, methyl propionate, ethyl propionate may be used.
[47]
At this time, the lithium salt is a material that is readily soluble in non-aqueous liquid electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB10Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
[48]
[49]
With reference to Figure 3 to Figure 5, the lithium electrode material supply 130 is provided in plurality it can be accommodated in a battery case (110). Here, the lithium material supply electrode 130 to the first lithium material supply electrode 131 and the electrode the other side the second lithium refeed electrode 132 is positioned on assembly 120 to be positioned on one side of the electrode assembly 120, It can be included. In this case, the electrode assembly 120 in the receiving part of the battery case 110 is positioned, in a receiving space located at both sides of the electrode assembly 120, the first lithium material supply electrode 131 and the second lithium material supply electrode (132 ) it can be located.
[50]
In addition, the electrically lithium refeed electrode lead (133 134) connected to the material supply lithium electrode 130 may be further provided.
[51]
In addition, the lithium electrode material supply 130, for example, may be made of lithium metal (Metal).
[52]
On the other hand, a plurality of lithium refeed electrode 130 may be provided surrounding the said respective side end portions in the electrode assembly 120. In this case, the lithium electrode material supply 130, for example, be formed of a "c" shape. Here, the through-hole (131a) of the electrode tab through the lithium material supply electrode 130 can be formed.
[53]
On the other hand, the lithium material supply electrode tabs (135 136) protruding to the side of the lithium electrode material supply unit 130 may be further provided. Here, the lithium electrode material supply tabs (135 136) may be electrically connected to the lithium-electrode lead material supply (133 134). In this case, for example, lithium refeed electrode tabs (135 136) may be made of a lithium metal, a lithium electrode lead material supply (133 134) it may be formed of aluminum material.
[54]
Then, the lithium material supply electrode tabs (135 136) and lithium refeed electrode lead (133 134) can be mutually fixed by welding.
[55]
In addition, located in the interior of the lithium material supply electrode 130 and the lithium material supply electrode tabs (135 136) is a battery case (110) is accommodated therein, the lithium material supply electrode leads (133 134), one end portion the battery case 110 of the and, the other side may be projected to the outside of the battery case (110).
[56]
[57]
The discharge step may be discharged to the electrode 123 prior to the lithium material supply step. Here, the discharge step to discharge possible through the full movement of the lithium ions of the cathode 122 to the anode 121. The In other words, it is possible to move the lithium ions in the cathode 122 to the anode 121. The
[58]
[59]
Lithium resupply step is lithium refeed electrode 130 is further provided with a secondary battery 100, the positive electrode 121, a counter electrode (Counter electrode) to set, and the lithium material supply electrode 130, the working electrode (Working set to the electrode) to be charged lithium ions to the positive electrode 121 via the lithium electrode material supply (130). Here, the working electrode is an electrode for supplying lithium ions, the counter electrode is an electrode that receive lithium ions.
[60]
Here, the lithium material supply step is electrically turned on (on) between the between the anode 121 and the cathode 122 electrically off (off) and a lithium material supply electrode 130 and a cathode 122. The That is, when the lithium secondary battery 100 is used in electronic devices lithium refeed electrode 130 off as the electrical (off) and the positive electrode 121 and negative electrode 122 is electrically on (on) maintain state but , lithium secondary batteries electrically on (on) the lithium material supply electrode 130 and the cathode 122 when to restore the capacity of (100), and sets the positive electrode 121 in the off (off) state. In this case, the electrical connection between the cathode lead 125 is connected to the anode 121, cathode 122, anode lead 126, and a lithium material supply electrode lithium refeed electrode lead (133 134) associated with the (130) associated with each individual the on / from the turning off the anode 121, cathode 122, and a lithium material supply electrode 130 may be selectively electrically on / off.
[61]
[62]
On the other hand, the lithium material supply step, for example, set from a plurality of lithium refeed electrode 130 provided in any of the lithium material supply electrode 130 to the working electrode is charged lithium ions to the positive electrode 121, a cathode ( 121), the capacity is 40 to 60% is any one of a lithium material supply electrode 130, instead of the other one of the lithium material supply electrode 130 to be fully charged lithium ions to the positive electrode 121 is set to the working electrode when the have.
[63]
Here, the lithium material supply step, and more specifically, for example, charging the lithium ion to the positive electrode 121 by setting the first lithium refeed electrode 131 is positioned in the one side direction of the electrode assembly 120 with the working electrode, When the filling amount of the positive electrode 121 is 50% may be the fully-charged lithium ions instead of the first lithium material supply electrode 131 by setting the second lithium material supply electrode 132 to the working electrode to the positive electrode 121. the
[64]
Accordingly, by using both the first lithium material supply electrode 131 and the second lithium refeed electrode 132 located on both sides of the electrode assembly 120 supplies the lithium ions in the positive electrode 121, a positive electrode (121 ) it can be supplied evenly to the lithium ions. That is, when supplying lithium source only to one side of the anode 121, but a lithium source shifted the supply side, it is possible to supply the lithium source than when evenly supply the lithium source to both sides of the positive electrode 121. The
[65]
[66]
Cathode discharge step is to set up and then re-supply the lithium ion to the anode 121 via the lithium material supply step, setting the lithium material supply electrode 130 to the counter electrode, and the negative electrode 122 as the working electrode, the cathode ( 122) to thereby completely discharged to a discharge limit. That is, to move the lithium ions remaining in the cathode 122 to supply the lithium electrode material 130. Therefore, it is possible to move it does not move to the anode 121 from the cathode 122 to the capacity limit of the positive electrode 121, lithium ions remaining lithium ions in the lithium electrode material supply (130). In the end, removing the lithium ions remaining in the cathode 122 and is capable of supplying new lithium ion.
[67]
In this case, by repeating the lithium material supply step and the discharge step the anode and increase the electrode capacity, it is possible to supply the new lithium.
[68]
[69]
On the other hand, the negative electrode discharge step from the lithium material supply electrodes 130 provided in plurality to set either one of the lithium material supply electrode 130 to the counter electrode and the discharge of the negative electrode 122, the discharge amount of the negative electrode 122 of 40 to When the 60% which can be fully discharged to a lithium electrode material supply 130 instead of the cathode 122 by setting the other of the lithium material supply electrode 130 to the counter electrode.
[70]
Here, the cathode discharge step is more specifically, for example, the electrode assembly 120, the first lithium material supplied from the negative electrode 122, a first lithium refeed electrode 131 is positioned in the one side direction to set the counter electrode of the electrode ( 131) to when the discharge amount is 50% of the first lithium refeed electrode 131 instead of the second lithium material supply electrode 132 by setting the counter electrode the cathode (122 and discharged by the movement of the lithium ions, a negative electrode (122) ) it can be completely discharged from the lithium ion.
[71]
[72]
Cathode discharge step in regeneration method of an embodiment The lithium secondary battery of the present invention includes a pulse applying step of removing the inorganic salt layer and organic salt layer deposited on the cathode 122 by applying a high current pulse to the cathode 122, more can do.
[73]
More specifically, the cathode discharge phase is a secondary battery (100) using repeated as a result, thicker cathode 122 to the inorganic salt layer and organic salt layer to the negative electrode 122, the movement of lithium ion velocity by applying a strong high-current pulse to the by increasing the can separated from the cathode 122.
[74]
That is, inorganic salt layer formed on the outer surface of the lithium salt is inorganic salt and organic salt are repeated as the negative electrode 122 is laminated on the outer surface to form a layer (layer), the cathode 122 along the discharge contained in the electrolytic solution, and when the organic salt layer will block the movement of the lithium ions is located in the negative electrode active material in the negative electrode 122, by applying a strong high-current pulse to the cathode 122 by increasing the moving speed of the lithium ions, covering the outer surface of the negative electrode active material inorganic salt layer, and it is possible to leave the inorganic salt and organic salt layer on the cathode layer 122 is an organic salt layer taking lithium ions are pushed.
[75]
Here, by the pulse magnitude of the current is proportional to the moving speed of lithium ion, is more a pulse magnitude of the current steel increase the moving speed of the lithium ions, and applying a strong high-current pulse to inorganic size remaining in the anode 122 larger salt you can remove the layer and the organic salt layer.
[76]
Then, the pulse applying step may be applied specifically, for example, a 1.0 ~ 2.5C current pulse to the cathode 122. Here, when applying a low current pulse than 1.0C on the negative electrode 122 is lower the moving speed of the lithium ions may be less an effect of the inorganic salt and the organic layer salt layer removed.
[77]
Then, when applying a high current pulse than 2.5C on the negative electrode 122, and due to the excessive high current can be a negative electrode active material damage or destruction. In addition, upon application of the high current pulse than 2.5C on the negative electrode 122, due to the excessive high current cathode (122) said surface layer SEI (Solid electrolyte interface) for lithium ions to be broken, which is formed a dead lithium (dead) DEN dendrite can be grown in (dendrite) increasing the resistance, wherein the continuously dendrite is grown as by damaging the membrane 124, an anode 121 and a cathode 122, a short circuit is a risk of fire or explosion may occur as have.
[78]
At this time, it is possible to apply a more specific example, 2.5C the cathode current pulse (122) of (If the battery capacity is applied to 50Ah, and the current of 2.5C, 50 * 2.5 = a current of 125A flows) .
[79]
Then, the applied pulse applying step when the discharge of the negative electrode 122 is included in the negative electrode discharge phase, the setting from the lithium material supply electrode 130 provided with a plurality of any of the lithium material supply electrode 130 to the counter electrode pulse these steps, and when the amount of discharge of the cathode 122 is 40 to 60% by either setting a single lithium refeed electrode 130 instead of the other one of the lithium material supply electrode 130 to the counter electrode the steps is pulse and can be completely discharged, the cathode (122). In this way, the mobile lithium ion in the positive electrode 121 that is moved by the pulse application step to the strong current, and it is possible to prevent a problem that the positive electrode structure in accordance with the decay compromising or destroying the positive electrode active material.
[80]
[81]
Determination step is lithium refeed set the electrode 130 to the working electrode, the positive electrode 121 and negative electrode 122, the counter by setting the electrode, lithium refeed a positive electrode 121 and the negative electrode based on the electrode 130 It can be detected by the respective voltage values ​​and the charging capacity of 122, to determine the degree of degradation of the positive electrode 121 and negative electrode 122. the
[82]
Here, the anode 121 and the cathode when over 122 measures the voltage value and the charge capacity can not measure voltage and charge capacity for each of the positive electrode 121 and negative electrode 122. The Only, the positive electrode 121 and negative electrode 122 is be made of a single electrical connection to display the only one voltage value and the charging capacity.
[83]
However, setting the lithium material supply electrode 130 to the reference electrode, connected to the lithium material supply electrode 130 and positive electrode 121, it can be connected to the lithium material supply electrode 130 and negative electrode 122 individually the voltage value and the charge capacity of the positive electrode 121 and negative electrode 122 can be measured separately. As a result, the degree of degradation of the positive electrode 121 and negative electrode 122 via the lithium material supply electrode 130, respectively can be accurately determined in the individual.
[84]
Figure 6 is a graph of the Differential voltage data used in the determination step in the regeneration of a lithium secondary battery according to an embodiment of the invention.
[85]
The X axis also indicates the charge capacity (Capacity) in the graph of 6, Y axis represents the Differential voltage (dQ / dQ). Here, Y axis Differential voltage indicates that the value obtained by dividing the differential voltage of the negative (dV) with a derivative of the charge capacity of the negative value (dQ). Then, the graph of Fig. 6 can be divided into A, B, C, D zone along the charge capacity.
[86]
, B and C section shown in Figure 6 is Shifting to the right on the graph of Figure 6 if the active material is degraded, D zone is Shifting to the right side is reduced to the available lithium in a lithium secondary battery.
[87]
Therefore, it is possible to check the degree of degradation, the amount of soluble lithium in the active material through the graph shown in Figure 6 can accurately determine the degradation tendency of the secondary battery.
[88]
On the other hand, it may be represented anode Differential voltage graph as a cathode Differential voltage graph shown in Fig. After all, a negative electrode, it is possible to measure separately the data of the positive electrode, it is possible to determine the degree of degradation of the positive electrode and the negative electrode individually.
[89]
In particular, it is possible to supply lithium in a required time by monitoring the Differential voltage graph of the positive and negative electrodes in real time.
[90]
[91]
If also refer to 3 to 5, the balance redefining step is lithium supply amount and the cathode discharge of the positive electrode 121 and negative electrode 122, positive electrode 121, through to determine the degradation degree, the lithium material supply step of using a discrimination step adjusting the discharge amount of the negative electrode 122 through the steps can be re-establish the balance of the electrode 123.
[92]
Than when in detail, via the determining step the cathode 122, it is determined that more are conducted further degradation degree of the positive electrode 121, and by increasing the lithium supply amount through the lithium material supplying step corresponding to the capacity of the positive electrode 121 and negative electrode 122 It controls the direction.
[93]
On the other hand, if it is determined that the degradation degree is advanced further in the cathode 122 than the anode 121 via the determination step, the direction in which to increase the lithium discharge amount through the cathode discharge period corresponding to the capacity of the positive electrode 121 and negative electrode 122 be adjusted.
[94]
That is, the positive electrode 121 and negative electrode 122 of the lithium when the ion is moved when performing charge and discharge, the anode 121 or the cathode 122 receives any one of the capacity of the electrode 123 is restricted among the other of can be solved in that the limiting capacity of the electrode 123. Eventually it is possible to increase the effective capacity of the secondary battery 100 more.
[95]
[96]
7 is a graph showing a resistance change of the lithium secondary battery regenerated to the regeneration method of a lithium secondary battery according to an embodiment of the invention.
[97]
The graph shown in 7 shows the resistance change of the lithium secondary battery The lithium secondary regenerated to the regeneration method of the battery (A) and before regenerating the lithium secondary battery (B) according to an embodiment of the invention. Here, the horizontal axis of the graph SOC; tanae out the (State of Charge state of charge), and the vertical axis indicates the resistance (Resistance). Then, the application of the graph 1.5C (Coulomb) electricity in the lithium secondary battery of Figure 6 was detected in the resistance value of 98.7A when the current flows in the lithium secondary battery. At this time, the resistance value was detected in each section by lowering the electric 10 seconds in each section of the charge.
[98]
If also refer to the graph shown in Figure 7, shows that the resistance of the lithium secondary lithium secondary battery (A) regenerated to the regeneration method of a battery according to an embodiment of the present invention reduced the resistance of the regenerative pre lithium secondary battery (B) can. After all, it can be seen that the performance of lithium secondary battery The lithium secondary battery (A) of the regeneration by the regenerative method in accordance with an embodiment of the present invention an improved
[99]
[100]
In the following, with reference to FIG 1 to FIG 5, will be described in the regeneration method of a lithium secondary battery according to another embodiment of the present invention.
[101]
If also refer to 1 to 5, the regeneration method of a lithium secondary battery according to another embodiment of the present invention may differ in as compared to the regeneration method of the lithium secondary battery according to the above-described example, the determination method of the determination step . Thus, the present embodiment is the same as information, an embodiment will be briefly described, and the technique with the focus on the differences.
[102]
Discrimination method in the regeneration of a lithium secondary battery according to another embodiment of the present invention is a lithium material supply, based on the electrode 130, positive electrode 121 and to the constant current pulse to a negative electrode (122) is a certain amount of time, adding the current the value and detecting the respective resistance values ​​anode 121 and the cathode 122 through the variation value of the voltage, the resistance of the larger the positive electrode 121 and negative electrode 122 in a manner that is determined to be more cost much degeneration it is possible to determine the degree of degradation.
[103]
Here, the determination method, for example, 1C current pulse to the anode 121 and the cathode 122 (Applying if a battery capacity of 50Ah, 1C current pulse, the 50 * 1 = 50A current to flow), 10 sec while there may through the current value and the variation value of the voltage is added to the detection of each of the resistance values ​​anode 121 and the cathode 122. the
[104]
[105]
On the other hand, according to the degradation degree of the positive electrode 121 and negative electrode 122 it is determined by the regeneration method of a lithium secondary battery via the determination step in the balance re-establish phase according to another embodiment of the present invention, the positive electrode through the lithium material supply step ( 121) can be adjusted by the discharge amount of the negative electrode 122 via the lithium supply amount and the cathode discharge phase, re-establish the balance between the positive electrode 121 and negative electrode 122 of the.
[106]
[107]
Above been described in detail throughout the present invention to a particular embodiment, This is to be described in detail the present invention, the regeneration method of the lithium secondary battery of the present invention is not limited to this. The various embodiments by those skilled in the art within the spirit of the present invention will be that it is possible.
[108]
In addition, the specific scope of protection of the invention will become clear by the following claims.

Claims

[Claim 1]A regeneration method of a secondary battery including a battery case, the electrode and the separator are mobilized alternately stacked electrode assembly and formed portion receiving for receiving the electrode assembly including a positive electrode and a negative electrode, the lithium material supply electrode is further in the secondary battery is provided, the lithium material supply step of setting the anode as a counter electrode, and, by setting the lithium supply material as the working electrode (Working) electrodes, charge the lithium ions into the positive electrode through the lithium electrode material supply; And a negative electrode which was re-supply lithium ions to the positive electrode through the lithium material supply step, setting the lithium material supply electrode as the counter electrode and, by setting the anode as a working electrode, a full discharge of the negative electrode to discharge limit and, regeneration of a lithium secondary battery to restore the capacity of the secondary battery including the discharge phase.
[Claim 2]
The method according to claim 1, before the lithium material supply step, the regeneration method for a lithium secondary battery, the negative electrode further comprises a discharge step of discharging the discharging electrode by the movement of the lithium ions into the positive electrode.
[Claim 3]
The method according to claim 1, performing the above-mentioned lithium material supply step and the cathode discharge phase repeatedly, regeneration of a lithium secondary battery to restore the capacity of the secondary battery.
[Claim 4]
The method according to claim 1, wherein the lithium resupply step is set to any one of the lithium material supply electrode to the working electrode charge the lithium ions into the positive electrode from the lithium material supply electrode provided in plurality, and the filling amount of the positive electrode 40 to 60% wherein any one of the lithium electrode instead of the re-supply by setting a different one of the lithium electrode material supplied to the working electrode of a lithium secondary battery regeneration of fully charged lithium ions to the positive electrode when the.
[Claim 5]
The method according to claim 1, wherein the cathode discharge step is one wherein in the lithium material supply electrode provided with a plurality of sets any one of the lithium material supply electrode as the counter electrode and the discharge to the cathode, the amount of discharge of the negative electrode when the 40-60% regeneration method of a lithium secondary battery of a lithium electrode instead of the re-supply by setting a different one of the lithium electrode material supplied to the counter electrode to fully discharge the cathode.
[Claim 6]
The method according to claim 4 or claim 5, wherein the plurality of lithium refeed electrode is lithium and a second lithium material supply electrode which is located at the other end of the first lithium material supply electrode and the electrode assembly being located to one side of the electrode assembly of a secondary regenerative method of the battery.
[Claim 7]
The method according to claim 4 or claim 5, wherein the cathode discharge step regeneration method of the lithium secondary battery further comprising: a pulse applying step for applying a high current pulse to the cathode to remove the inorganic salt and organic salt layer deposited on the negative electrode layer.
[Claim 8]
The system according to claim 7, wherein the pulse applying step from 1.0 to 2.5 regenerating method of a lithium secondary battery C current pulse to be applied to the cathode.
[Claim 9]
A method according to any one of claims 1 to 5, wherein the positive electrode, and further comprises a determination step that determines the degradation level of the negative electrode, it is determined via the determination step is degraded degree of the positive electrode and the negative electrode only when more than a predetermined range regeneration method of a lithium secondary battery to perform any one or more of the steps in the lithium material supply step or the cathode discharge phase.
[Claim 10]
The method according to claim 9, to determine the positive electrode and the degradation level of the negative electrode via the determination step, by controlling the discharge amount of the negative electrode through the lithium supply amount and the cathode discharge phase to said positive electrode through the lithium material supply step regeneration method of a lithium secondary battery further comprises the step of re-establish the balance re-establish the balance between the electrodes.
[Claim 11]
The method according to claim 9, wherein the determining step is the lithium material supply electrode to set the working electrode, and setting the positive electrode and the negative electrode as a counter electrode, each voltage of the positive electrode and the negative electrode with respect to the lithium material supply electrode value and the regeneration method of detecting the charge capacity of the lithium secondary battery to determine the degree of degradation of the positive electrode and the negative electrode.
[Claim 12]
The method according to claim 9, wherein the determining step each with respect to the lithium material supply electrode, by applying the positive electrode and the constant a constant current pulse time in the negative, adding the current value and the voltage of the positive electrode and the negative electrode through a change in the value of detected, regeneration of a lithium secondary battery to determine the degree of degradation of the positive electrode and the negative electrode in such a way that this determines that the resistance value of the larger degradation is more resistance.
[Claim 13]
A method according to any one of claims 1 to 5, wherein the lithium electrode material is supplied regeneration method of a lithium secondary battery comprising a lithium metal (Metal).