Title of Invention: Lithium Secondary Battery Activation Method and Lithium Secondary Battery
technical field
[One]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0121825 filed on September 21, 2020, and all contents disclosed in the Korean Patent Application Document are incorporated as a part of this specification.
[2]
[3]
The present invention relates to a method for activating a lithium secondary battery and a lithium secondary battery.
[4]
background
[5]
As technology development and demand for mobile devices increase, the demand for secondary batteries as an energy source is rapidly increasing. Among these secondary batteries, a lithium secondary battery having a high energy density and voltage, a long cycle life, and a low self-discharge rate has been commercialized and widely used.
[6]
In general, a lithium secondary battery is manufactured by the following method. A composition for forming an electrode active material layer including an electrode active material is applied on an electrode current collector and dried to prepare electrodes (positive and negative electrodes), an electrode assembly is formed by interposing a separator between the positive electrode and the negative electrode, and then this electrode Insert the assembly into the cell case and seal. In addition, in order to determine whether the secondary battery is defective and secure the performance of the secondary battery, in particular, stability of lifespan, an activation process is always performed before product shipment. The activation process is to activate the battery and remove gas by repeating charging and discharging. On the other hand, when charging a secondary battery, lithium ions from lithium metal oxide used as a positive electrode move and are inserted into a carbon (crystalline or amorphous) electrode used as a negative electrode. At this time, lithium has high reactivity, so Li 2 CO 3 , LiO , LiOH, etc. In addition , the compound such as Li 2 CO 3 , LiO, and LiOH forms a solid electrolyte interface (SEI) film on the surface of the anode. On the other hand, irreversibility of the positive electrode and the negative electrode occurs due to the solid electrolyte interfacial film. Accordingly, there is a problem in that the energy density of the lithium secondary battery is reduced.
[7]
To prevent this, there is a method of using Li 2 NiO 2 as a sacrificial cathode material . However, Li 2 NiO 2 has an orthorhombic structure in which the space group is Immm in the lithium secondary battery in which the activation process is completed, and after the activation process, the structure changes in three steps (the space group is Immm) within the usable voltage range. Phosphorus orthorhombic structure -> a trigonal structure with a space group of R-3m -> a monoclinic structure with a space group of C2/m), there is a problem in that impurities or gases are generated.
[8]
Accordingly, there is a need for a method capable of solving the problem of generating impurities or gases within an available voltage range.
[9]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
An object of the present invention is to provide a method for activating a lithium secondary battery capable of controlling the crystal structure of a sacrificial cathode material so that a side effect of the sacrificial cathode material occurring within an available voltage range is minimized.
[11]
means of solving the problem
[12]
The present invention relates to a first step of preparing a secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, which is represented by the following Chemical Formula 1 and includes a sacrificial positive electrode material having an orthorhombic structure; and a second step of maintaining the secondary battery at a voltage of 3.2V or higher for a predetermined time after charging the secondary battery.
[13]
[Formula 1]
[14]
Li 2 Ni 1-x M x O 2
[15]
M is at least one selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta and W;
[16]
0≤x<0.9.
[17]
[18]
In addition, the present invention provides a secondary battery comprising a positive electrode including a sacrificial positive electrode material represented by the following Chemical Formula 2, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, wherein the sacrificial positive electrode material has a trigonal structure in a discharged state It provides a single-phase lithium secondary battery having a.
[19]
[Formula 2]
[20]
LiNi 1-x M x O 2
[21]
M is at least one selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta and W;
[22]
0≤x<0.9.
[23]
Effects of the Invention
[24]
The lithium secondary battery activation method of the present invention includes a process of changing the crystal structure of the sacrificial cathode material from an orthorhombic structure to a trigonal structure, so that lithium ions can be easily replenished during initial charging, and side reactions (side reactions) within the available voltage range A sacrificial cathode material having a crystal structure capable of minimizing effect) may be provided.
[25]
Brief description of the drawing
[26]
1 is a view showing XRD patterns measured using in-situ XRD for a sacrificial cathode material during activation of a secondary battery and a sacrificial cathode material while charging an activated secondary battery in Example 1;
[27]
2 is an XRD pattern measured using ex-situ XRD for the sacrificial cathode material included in the secondary battery after charging the secondary battery of Comparative Example 1 that has completed the existing activation process to SOC 30, 60, and 90; It is the drawing shown.
[28]
3 is a view showing the volume of gas generated in the process of performing an initial reference performance test of each of the secondary batteries of good quality manufactured in Example 1 and Comparative Example 1. Referring to FIG.
[29]
Best mode for carrying out the invention
[30]
Hereinafter, the present invention will be described in more detail.
[31]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[32]
[33]
Lithium secondary battery activation method
[34]
The lithium secondary battery activation method according to the present invention is represented by the following Chemical Formula 1 and includes a positive electrode including a sacrificial positive electrode material having an orthorhombic structure, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte to prepare a secondary battery Step 1; and a second step of maintaining the secondary battery at a voltage of 3.2V or higher for a predetermined time after charging the secondary battery.
[35]
[Formula 1]
[36]
Li 2 Ni 1-x M x O 2
[37]
In Formula 1,
[38]
M is at least one selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta and W;
[39]
0≤x<0.9.
[40]
[41]
The lithium secondary battery activation method may further include a pre-aging step of primary aging the secondary battery at room temperature before performing the second step.
[42]
In addition, the lithium secondary battery activation method may include: a room temperature aging step of secondary aging the secondary battery that has undergone the second step at room temperature; A high temperature aging step of tertiary aging of the secondary aged secondary battery at a high temperature; and a degas (degas) step of removing gas from the tertiary aged secondary battery.
[43]
The method may further include, after performing the degassing step, determining whether the secondary battery is defective.
[44]
[45]
Hereinafter, a method for activating a lithium secondary battery according to the present invention will be described in detail.
[46]
[47]
Step 1
[48]
The first step is a step of preparing a secondary battery including a positive electrode including a sacrificial positive electrode material represented by the following Chemical Formula 1 and having an orthorhombic structure, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte.
[49]
[Formula 1]
[50]
Li 2 Ni 1-x M x O 2
[51]
M is at least one selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta and W;
[52]
0≤x<0.9.
[53]
[54]
In the sacrificial cathode material, a crystal structure of the sacrificial cathode material may be completely converted from an orthorhombic structure to a trigonal structure through the second step.
[55]
The sacrificial cathode material is a material for compensating for lithium ions consumed in the formation of an SEI layer or a by-product. The sacrificial cathode material is a material in which lithium is easily desorbed, and the sacrificial cathode material represented by Formula 1 and having an orthorhombic structure has a trigonal structure thermodynamically stable in an orthorhombic structure while lithium is desorbed through a second step to be described later. will be permanently changed to
[56]
[57]
Specifically, the secondary battery may include one or more unit electrodes including a positive electrode and a negative electrode, and an electrode assembly wound with a separator interposed between the unit electrodes may be embedded in a battery case. The secondary battery may be a cylindrical, prismatic, or pouch-type secondary battery.
[58]
The positive electrode and the negative electrode may be prepared by applying a composition for forming an active material layer including an electrode active material on a current collector, respectively, and then drying the composition.
[59]
The composition for forming the positive electrode active material layer may optionally further include a binder, a conductive material, a filler, and the like, if necessary, in addition to the sacrificial positive electrode material and the positive electrode active material represented by Formula 1 and having an orthorhombic structure. In addition to the anode active material, the composition for forming the anode active material layer may optionally further include a binder, a conductive material, a filler, and the like, if necessary.
[60]
The current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, carbon on the surface of copper or stainless steel. , nickel, titanium, silver, etc. surface-treated, aluminum-cadmium alloy, etc. may be used. In addition, the current collector may typically have a thickness of 3 μm to 500 μm, and may form fine concavities and convexities on the surface of the current collector to strengthen the binding force of the active material. For example, it may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam body, a nonwoven body, and the like.
[61]
The positive active material is a material capable of causing an electrochemical reaction, and as a lithium transition metal oxide, includes two or more transition metals, for example, lithium cobalt oxide (LiCoO 2 ) substituted with one or more transition metals (LiCoO 2 ), lithium layered compounds such as nickel oxide (LiNiO 2 ); lithium manganese oxide substituted with one or more transition metals; Formula LiNi 1-y M y O 2 , where M = Co, Mn, Al, Cu, Fe, Mg, B, Cr, Zn or Ga, including at least one of the above elements, 0.01=y≤=0.7 ) a lithium nickel-based oxide represented by; Li 1+z Ni 1/3 Co 1/3 Mn 1/3 O 2 , Li 1+z Ni 0.4 Mn 0.4 Co 0.2 O 2Li 1+z Ni b Mn c Co 1-(b+c+d) M d O (2-e) A e (where -0.5≤z≤0.5, 0.1≤b≤0.8, 0.1≤c≤ 0.8, 0≤d≤0.2, 0≤e≤0.2, b+c+d<1, M = Al, Mg, Cr, Ti, Si or Y, and A = F, P or Cl) lithium nickel cobalt manganese composite oxide; Formula Li 1+x M 1-y M' y PO 4-z X z where M = transition metal, preferably Fe, Mn, Co or Ni, M' = Al, Mg or Ti, X = F, S or N, and -0.5≤x≤+0.5, 0≤y≤0.5, 0≤z≤0.1 olivine-based lithium metal phosphate represented by), but is not limited thereto. The positive active material may be included in an amount of 80% to 99% by weight based on the total weight of the positive active material layer.
[62]
As the anode active material, a compound capable of reversible intercalation and deintercalation of lithium may be used. Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; metal compounds capable of alloying with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, or Al alloy; SiO β (0<β<2), SnO 2, a metal oxide capable of doping and dedoping lithium, such as vanadium oxide and lithium vanadium oxide; Alternatively, a composite including the metallic compound and a carbonaceous material such as a Si-C composite or a Sn-C composite may be used, and any one or a mixture of two or more thereof may be used. In addition, a metal lithium thin film may be used as the negative active material. In addition, as the carbon material, both low crystalline carbon and high crystalline carbon may be used. As low crystalline carbon, soft carbon and hard carbon are representative, and as high crystalline carbon, natural or artificial graphite of amorphous, plate-like, flaky, spherical or fibrous shape, and Kish graphite (Kish) graphite), pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, liquid crystal pitches (Mesophase pitches), and petroleum and coal tar pitch (petroleum or coal tar pitch) High-temperature calcined carbon such as derived cokes) is a representative example. The negative active material may be included in an amount of 80% to 99% by weight based on the total weight of the negative active material layer.
[63]
The binder is a component that assists in bonding between the conductive material, the active material, and the current collector, and is typically added in an amount of 0.1 wt% to 10 wt% based on the total weight of the active material layer. Examples of such binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro and roethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, nitrile-butadiene rubber, fluororubber, and various copolymers thereof.
[64]
The conductive material is a component for further improving the conductivity of the active material, and may be added in an amount of 10 wt% or less, specifically 5 wt% or less, based on the total weight of the active material layer. Such a conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery. For example, graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers and metal fibers; metal powders such as carbon fluoride, aluminum, and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives may be used.
[65]
[66]
On the other hand, in the lithium secondary battery, the separator separates the negative electrode and the positive electrode and provides a passage for lithium ions to move, and as long as it is used as a separator in a lithium secondary battery, it can be used without any particular limitation, especially for the movement of ions in the electrolyte It is preferable to have a low resistance to and excellent electrolyte moisture content. Specifically, a porous polymer film, for example, a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or these A laminate structure of two or more layers of may be used. In addition, a conventional porous nonwoven fabric, for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. In addition, in order to secure heat resistance or mechanical strength, a coated separator containing a ceramic component or a polymer material may be used, and may optionally be used in a single-layer or multi-layer structure.
[67]
[68]
In addition, the electrolyte may include, but is not limited to, an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte, which can be used in manufacturing a lithium secondary battery.
[69]
Specifically, the electrolyte may include an organic solvent and a lithium salt.
[70]
The organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move. Specifically, as the organic solvent, ester solvents such as methyl acetate, ethyl acetate, γ-butyrolactone, ε-caprolactone; ether-based solvents such as dibutyl ether or tetrahydrofuran; ketone solvents such as cyclohexanone; aromatic hydrocarbon solvents such as benzene and fluorobenzene; dimethylcarbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate, carbonate-based solvents such as PC); alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles, such as R-CN (R is a C2-C20 linear, branched, or cyclic hydrocarbon group, and may contain a double bond aromatic ring or an ether bond); amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane; Or sulfolane may be used. Among these, carbonate-based solvents are preferred, A cyclic carbonate (eg, ethylene carbonate or propylene carbonate, etc.) having high ionic conductivity and high dielectric constant capable of increasing the charge/discharge performance of a battery, and a low-viscosity linear carbonate-based compound (eg, ethylmethyl carbonate, dimethyl carbonate or diethyl carbonate, etc.) is more preferable. In this case, when the cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9, the performance of the electrolyte may be excellent.
[71]
[72]
The lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery. Specifically, as an anion of the lithium salt, F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C - , CF 3 (CF 2 ) 7 SO 3 - , CF 3 CO 2 - , CH 3 CO 2 - , SCN -and (CF 3 CF 2 SO 2 ) 2 N − may be at least one selected from the group consisting of, and the lithium salt is, LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(C 2 F 5 SO 3 ) 2 , LiN(C 2 )F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2. LiCl, LiI, or LiB(C 2 O 4 ) 2 , etc. may be used. The concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, excellent electrolyte performance may be exhibited, and lithium ions may move effectively.
[73]
[74]
In addition to the electrolyte components, the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, tri Ethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida One or more additives such as jolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be further included. In this case, the additive may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.
[75]
[76]
Step 2
[77]
The second step is a step of changing the crystal structure of the sacrificial cathode material from an orthorhombic structure to a trigonal structure by maintaining the secondary battery at a voltage of 3.2V or higher for a predetermined time after charging the secondary battery.
[78]
Specifically, in the second step, the secondary battery is subjected to a C-rate of 0.025C to 0.2C, preferably at a C-rate of 0.05C to 0.2C, more preferably at a C-rate of 0.05C to 0.15C. It may be a step of changing the crystal structure of the sacrificial cathode material from an orthorhombic structure to a trigonal structure by maintaining a constant voltage for a predetermined time after charging at a rate. On the other hand, when the C-rate is less than 0.020C, the charging time increases and the total time required for the activation process increases. Overvoltage may occur, and there is a problem in that it is difficult to form a uniform SEI film.
[79]
After charging the secondary battery to 3.2V or more, preferably 3.5V to 4.0V, more preferably 3.6V to 3.9V, even more preferably 3.7V to 3.9V, within the same voltage range for a certain time During holding, the sacrificial anode material having an orthorhombic structure is permanently changed to a sacrificial cathode material having a trigonal structure.
[80]
The time for maintaining the voltage in the second step may be 30 minutes or more, preferably 30 minutes to 6 hours, preferably 1 hour to 6 hours, more preferably 2 hours to 5 hours. On the other hand, if the time for maintaining the voltage is less than 30 minutes, the crystal structure change of the sacrificial cathode material may not completely occur, and if it exceeds 6 hours, the activation process time may increase and productivity may decrease.
[81]
In the second step, for example, after charging to 3.8V at a C-rate of 0.1C, and maintaining the voltage at 3.8V for 3 hours, a sacrificial cathode material having an orthorhombic structure having a space group of Immm is applied to a space group. This may be a step of changing into a trigonal structure, which is R-3m.
[82]
The crystal structure of the sacrificial cathode material that has undergone the second step is permanently changed to a trigonal structure.
[83]
The sacrificial cathode material that has undergone the second step may be a single phase having a trigonal structure.
[84]
In the sacrificial cathode material that has undergone the second step, only a crystal structure change between a trigonal structure and a monoclinic structure may occur within an available voltage range (eg, 2.5V to 4.2V) in which an actual battery is implemented. Accordingly, the three-stage structural change (orthorhombic structure with space group Immm -> trigonal structure with space group R-3m -> monoclinic structure with space group C2/m) does not occur, In the lithium secondary battery that has undergone the activation process according to the present invention, the content of gas generated when stored for a long time at room temperature and high temperature may be reduced.
[85]
[86]
The sacrificial cathode material having the trigonal structure may be represented by the following formula (2).
[87]
[Formula 2]
[88]
LiNi 1-x M x O 2
[89]
In Formula 2,
[90]
M is at least one selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta and W;
[91]
0≤x<0.9.
[92]
[93]
pre-aging stage
[94]
The pre-aging step is a step of primary aging the secondary battery at room temperature before performing the second step. Specifically, the pre-aging step is a step of leaving the secondary battery at room temperature for a specific time so that the battery is impregnated with the injected electrolyte.
[95]
The pre-aging may be performed at room temperature and under normal pressure conditions so that the electrolyte can permeate the positive and negative electrodes well, and for 24 hours to 72 hours, preferably for 30 hours to 50 hours, more preferably for 40 hours. to 50 hours.
[96]
[97]
room temperature aging step
[98]
In the room temperature aging step, the lithium secondary battery activation method is a step of secondary aging the secondary battery that has undergone the second step at room temperature.
[99]
Through the aging step at room temperature, the SEI film is more stabilized and formed with an even and uniform thickness without partial bias. That is, it is generally stabilized by leaving it at room temperature for a certain period of time. Aging at room temperature improves the electrode impregnation property of the battery electrolyte and thereby secures the capacity reliability of the battery.
[100]
The room temperature aging may be performed for 24 hours to 72 hours, preferably for 30 hours to 50 hours, and more preferably for 40 hours to 50 hours.
[101]
[102]
high temperature aging step
[103]
The high temperature aging step is a step of tertiary aging of the secondary aged secondary battery at a high temperature. The high-temperature aging step is also a process that allows the SEI film to be more stabilized and uniformly formed by thermal energy and electrochemical energy.
[104]
The high temperature aging may be carried out at 40°C to 80°C, preferably at 50°C to 70°C, more preferably at 55°C to 65°C. If the high-temperature aging temperature is less than 40°C, additional stabilization of the SEI film does not proceed easily. This lowering problem occurs.
[105]
The high temperature aging may be performed for 12 hours to 48 hours, preferably for 20 hours to 40 hours, and more preferably for 20 hours to 30 hours.
[106]
[107]
degas step
[108]
The degassing step is a step of removing gas from the tertiary aged secondary battery.
[109]
This is to remove the side reaction gas generated inside the battery through the aging step, and it is possible to remove the side reaction gas generated inside the secondary battery through the degassing step. Since the gas generated in the aging step may cause swelling of the battery, the gas may be removed through a degassing process. The degassing process may be performed by opening the sealing of the battery case or by providing a separate gas removal mechanism.
[110]
[111]
Determining whether the secondary battery is defective
[112]
The step of determining whether the secondary battery is defective is to check whether the secondary battery is abnormal, and may be performed using charge/discharge capacity data obtained by performing charging and discharging in an available voltage range of the secondary battery.
[113]
Specifically, the step of determining whether the secondary battery is defective may include: checking the capacity of the battery with charge/discharge capacity data obtained while charging and discharging at 2.5V to 4.2V at a C-rate of 0.1C; and confirming the capacity of the battery with charge/discharge capacity data obtained while charging and discharging at 2.5V to 4.2V at a C-rate of C/3, which is a charge/discharge rate used in electronic products.
[114]
On the other hand, the lithium secondary battery manufactured according to the activation method of the present invention has a capacity when charging and discharging at a C-rate of C/3 is 97% or more of the capacity when charging and discharging at a C-rate of 0.1C. can
[115]
[116]
lithium secondary battery
[117]
A lithium secondary battery according to the present invention includes a positive electrode including a sacrificial positive electrode material represented by the following Chemical Formula 2, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte.
[118]
[Formula 2]
[119]
LiNi 1-x M x O 2
[120]
In Formula 2,
[121]
M is at least one selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta and W;
[122]
0≤x<0.9.
[123]
[124]
The sacrificial cathode material represented by Formula 2 and having a trigonal structure may be a single phase having a trigonal structure. A sacrificial cathode material having a trigonal structure represented by Chemical Formula 2 can be manufactured by controlling the synthesis conditions when synthesizing the sacrificial cathode material. It appears as a mixed state of the political system. However, when the crystal structure of the sacrificial cathode material is changed in a method of maintaining charge for a certain time in a voltage range of 3.2V or more in the activation process as in the present invention, a single-phase trigonal structure in which orthorhombic systems are not mixed can be formed. . When the sacrificial cathode material contains a part of an orthorhombic crystal structure, a three-step crystal structure change occurs between orthorhombic, trigonal, and monoclinic during battery charging and discharging, thereby reducing the effect of suppressing impurities and/or gas.
[125]
In contrast, since the sacrificial cathode material included in the secondary battery of the present invention consists of a trigonal single phase, a trigonal structure and a monoclinic structure within an available voltage range (eg, 2.5V to 4.2V) in which the actual battery is realized. Only changes in the crystal structure of the liver can occur. Accordingly, the three-stage structural change (orthorhombic structure with space group Immm -> trigonal structure with space group R-3m -> monoclinic structure with space group C2/m) does not occur, In the lithium secondary battery that has undergone the activation process according to the present invention, the content of gas generated when stored for a long time at room temperature and high temperature may be reduced.
[126]
In this case, the space group of the trigonal structure may be R-3m, and the space group of the monoclinic structure may be C2/m.
[127]
[128]
On the other hand, the sacrificial cathode material having a trigonal structure included in the secondary battery of the present invention has lattice parameters a, c, and γ of a unit cell of 2.8000Å≤a≤3.3000Å, 4.8000Å≤, respectively. c≤5.2000Å, γ=120°. In this case, lithium ions can be easily desorbed from the sacrificial cathode material during initial charging, and even when a crystal structure change between a trigonal structure and a monoclinic structure occurs within the usable voltage range in which an actual battery is realized, large distortion of the crystal structure ( distortion) does not occur, and side reactions can be minimized.
[129]
[130]
The lithium secondary battery may be a lithium secondary battery manufactured through the activation method according to the present invention.
[131]
Modes for carrying out the invention
[132]
Hereinafter, examples are given in order to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
[133]
[134]
production example
[135]
Li 2 NiO 2 having an orthorhombic structure with a space group of Immm as a sacrificial cathode material, LiNi 0.8 Co 0.1 Mn 0.1 as a cathode active material, carbon nanotubes as a conductive material, and PVdF as a binder in a weight ratio of 5.0:92.8:0.8:1.4 N- A positive electrode slurry was prepared by mixing in methyl-2-pyrrolidone (NMP) solvent. The positive electrode slurry was applied to one surface of an aluminum current collector, dried and then rolled to prepare a positive electrode.
[136]
Then, an anode active material mixed with artificial graphite and natural graphite in a weight ratio of 9:1, Super C65 as a conductive material, SBR as a binder, and CMC as a thickener in a weight ratio of 95.6:1.5:2.3:1.1 N-methyl-2- A negative electrode slurry was prepared by mixing in a pyrrolidone (NMP) solvent. The negative electrode slurry was applied to one surface of a copper current collector, dried and then rolled to prepare a negative electrode.
[137]
An electrode assembly was prepared by interposing a separator between the positive electrode and the negative electrode, and then placed inside the battery case, and then an electrolyte was injected to prepare a lithium secondary battery.
[138]
In this case, as the electrolyte, an electrolyte in which 1M LiPF 6 was dissolved in an organic solvent in which ethylene carbonate:ethylmethyl carbonate:diethyl carbonate was mixed in a volume ratio of 3:3:4 was used.
[139]
[140]
Example
[141]
Example 1
[142]
After pre-aging the secondary battery prepared in Preparation Example at room temperature for 24 hours, charging it to 3.8V at a C-rate of 0.1 C, and maintaining the voltage at 3.8V for 3 hours to change the crystal structure of the sacrificial cathode material in all directions It changed from a tetragonal structure to a trigonal structure. Then, the secondary battery including the sacrificial cathode material having a changed crystal structure was room temperature-aged at room temperature for 24 hours, and then high temperature-aged at 60° C. for 24 hours. After the high-temperature-aging secondary battery case was opened and degassed, the opened portion was resealed.
[143]
The capacity of the battery is checked with the charge/discharge capacity data obtained while charging and discharging at 2.5V to 4.2V at a C-rate of 0.1C, and 2.5V to 4.2 at a C-rate of C/3, the charge/discharge rate used in electronic products. By checking the capacity of the battery with the charge/discharge capacity data obtained while charging and discharging at V, a secondary battery of good quality was manufactured.
[144]
[145]
Comparative Example 1
[146]
After pre-aging the secondary battery prepared in Preparation Example for 24 hours at room temperature, the process of charging and discharging at room temperature at a C-rate of 0.1 C until SOC 30 was repeated three times. Then, the secondary battery including the sacrificial cathode material having a changed crystal structure was room temperature-aged at room temperature for 24 hours, and then high temperature-aged at 60° C. for 24 hours. After the high-temperature-aging secondary battery case was opened and degassed, the opened portion was resealed.
[147]
The capacity of the battery is checked with the charge/discharge capacity data obtained while charging and discharging at 2.5V to 4.2V at a C-rate of 0.1C, and 2.5V to 4.2 at a C-rate of C/3, the charge/discharge rate used in electronic products. By checking the capacity of the battery with the charge/discharge capacity data obtained while charging and discharging at V, a secondary battery of good quality was manufactured.
[148]
[149]
Experimental Example 1: X-ray diffraction (XRD) pattern measurement
[150]
During activation of the secondary battery in Example 1, using in-situ XRD (Empyrean, PANalytical) (X-ray source: Mo sealed tube, 60kV, 35mA), when starting charging at a C-rate of 0.1C XRD data measurements were performed on the sacrificial cathode material (I), the sacrificial cathode material (II) immediately after charging to 3.8V, and the sacrificial cathode material (III) after maintaining the voltage at 3.8V for 3 hours. In addition, while charging the secondary battery activated in Example 1 again at a C-rate of 0.1 C, in-situ XRD ( XRD data measurement was performed using Empyrean, PANalytical (X-ray source: Mo sealed tube, 60kV, 35mA). The resulting data is shown in FIG. 1 .
[151]
After charging the secondary battery of good quality prepared in Comparative Example 1 to SOC 30, 60, and 90 at a C-rate of 0.1 C, ex-situ XRD for the sacrificial cathode material included in the secondary battery (D8 Endeavor, Bruker) (X-ray source: Cu sealed tube, 40kV, 40mA) was used to measure XRD data, and the result data is shown in FIG. 2 .
[152]
Referring to FIG. 1 , it can be seen that (002) and (101) peaks, which are XRD peaks of the orthorhombic structure, disappear during the second step according to the present invention in Example 1. In addition, in the secondary battery activated according to the present invention, it can be confirmed that the sacrificial cathode material does not change to an orthorhombic structure while the secondary battery is being charged. That is, it can be seen that Li 2 NiO 2 having an orthorhombic structure does not exist in the sacrificial cathode material included in the secondary battery after activation according to the present invention.
[153]
In contrast, referring to FIG. 2 , since the (101) peak, which is the XRD peak of the orthorhombic structure, appears, the sacrificial cathode material included in the secondary battery after the conventional activation process is completed still has the orthorhombic structure of Li 2 NiO 2 It can be confirmed that there exists (the crystal structure of the sacrificial cathode material is sometimes an orthorhombic structure while charging the secondary battery). For reference, the reference data of FIG. 2 is XRD data of Li 2 NiO 2 having an orthorhombic structure in which the space group is Immm .
[154]
[155]
Experimental Example 2
[156]
For each of the secondary batteries of good quality manufactured in Example 1 and Comparative Example 1, an initial reference performance test (RPT) was performed, and the amount of gas generated during the initial reference performance test was measured by gas chromatography (gc agilent 7890b). was used, and the results are shown in Table 1 and FIG. 3 below.
[157]
[Table 1]
Gas generation (uL)
Example 1 450
Comparative Example 1 958
[158]
Referring to Table 1 and FIG. 3 , in the case of the secondary battery of Example 1 manufactured through the secondary battery activation method according to the present invention, only the sacrificial cathode material of the trigonal structure is included, and the structural change (space Since the orthorhombic structure with the group Immm -> the trigonal structure with the space group R-3m -> the monoclinic structure with the space group C2/m) does not occur, the initial reference performance test process It can be seen that the content of the gas generated in is significantly lower than that of the secondary battery of Comparative Example 1. Accordingly, in the lithium secondary battery activation method of the present invention, the crystal structure of the sacrificial cathode material is changed from an orthorhombic structure to a trigonal structure. It can be seen that it is possible to provide a sacrificial cathode material having a crystal structure capable of minimizing side reactions within an available voltage range, including the changing process.
Claims
[Claim 1]
A first step of preparing a secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, which is represented by the following Chemical Formula 1 and includes a sacrificial positive electrode material having an orthorhombic structure; and a second step of maintaining the secondary battery at a voltage of 3.2V or higher for a predetermined time after charging the secondary battery; a lithium secondary battery activation method comprising: [Formula 1] Li 2 Ni 1-x M x O 2 In Formula 1, M is at least one selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta and W, and 0≤x <0.9.
[Claim 2]
The method according to claim 1, wherein in the second step, the charging is performed up to 3.2V or more at a C-rate of 0.025C to 0.2C.
[Claim 3]
The method according to claim 1, wherein in the second step, the lithium secondary battery activation method is maintained for 30 minutes to 6 hours at a voltage of 3.2V or more.
[Claim 4]
The method according to claim 1, wherein in the second step, the secondary battery is charged to 3.5V to 4.0V, and then maintained at a voltage of 3.5V to 4.0V for 30 minutes to 6 hours.
[Claim 5]
The method according to claim 1, wherein the crystal structure of the sacrificial cathode material is changed from an orthorhombic structure to a trigonal structure through the second step.
[Claim 6]
The method according to claim 1, wherein the sacrificial cathode material subjected to the second step is a single-phase lithium secondary battery having a trigonal structure.
[Claim 7]
The method according to claim 1, wherein the sacrificial cathode material having a trigonal structure is represented by the following formula (2). [Formula 2] LiNi 1-x M x O 2 In Formula 2, M is Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd , Hf, Ta, and at least one selected from W, and 0≤x<0.9.
[Claim 8]
The method of claim 1 , further comprising a pre-aging step of primary aging the secondary battery at room temperature before performing the second step.
[Claim 9]
The method according to claim 1, room temperature aging step of secondary aging the secondary battery that has undergone the second step at room temperature; A high temperature aging step of tertiary aging of the secondary aged secondary battery at a high temperature; and a degassing step of removing gas from the tertiary-aged secondary battery.
[Claim 10]
The method of claim 9 , further comprising, after performing the degassing step, determining whether the secondary battery is defective.
[Claim 11]
The method according to claim 10, wherein the step of determining whether the secondary battery is defective comprises charging the secondary battery from 2.5V to 4.2V at a C-rate of 0.1C to 0.5C, and discharging from 4.2V to 2.5V. A lithium secondary battery activation method that is performed using the discharge capacity data.
[Claim 12]
A secondary battery comprising a positive electrode including a sacrificial positive electrode material represented by the following Chemical Formula 2, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, wherein the sacrificial positive electrode material is a single-phase lithium having a trigonal structure in a discharged state Secondary battery: [Formula 2] LiNi 1-x M x O 2 In Formula 2, M is Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, At least one selected from Ag, Cd, Hf, Ta and W, and 0≤x<0.9.
[Claim 13]
The lithium secondary battery according to claim 12, wherein the space group of the trigonal structure is R-3m.
[Claim 14]
The lithium secondary battery of claim 12 , wherein, in the sacrificial cathode material, only a crystal structure change between a trigonal structure and a monoclinic structure occurs in an available voltage range in which the lithium secondary battery operates.
[Claim 15]
The lithium secondary battery according to claim 14, wherein the space group of the monoclinic structure is C2/m.
[Claim 16]
The method according to claim 12, The sacrificial cathode material lattice constant (lattice parameter) of the unit cell (lattice parameter) a, c, γ values ​​of 2.8000Å≤a≤3.3000Å, 4.8000Å≤c≤5.2000Å, γ=120°, respectively phosphorus lithium secondary battery.