JP2014017210A - Lithium cuprate positive electrode material, method for producing the same, and lithium secondary battery including the positive electrode material as positive electrode active material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve discharge capacity and electrode potential of lithium cuprate that is a lithium secondary battery positive electrode material high in safety and excellent in cycle characteristics, thereby providing an inexpensive material for improving safety, energy density or cycle characteristics of a lithium secondary battery.SOLUTION: The present invention provides a positive electrode material for a lithium secondary battery, which is lithium cuprate having a crystal structure that belongs to a space group Immm and represented by a chemical formula: LiCuMO(where M represents metal, and 0.01≤x≤0.45 is satisfied).

Description

  The present invention relates to a lithium cuprate positive electrode material having a large discharge capacity and excellent cycle characteristics, a method for producing the positive electrode material, and a lithium secondary battery including the positive electrode material.

  Lithium secondary batteries, which are often used as power sources for portable small terminals, have high energy density and long cycle life, and are expected as backup power sources and energy buffers. A device to which a backup power source or an energy buffer is connected is generally a high drive voltage. When conventional lead batteries are used, the desired voltage is satisfied by connecting them in series, but a large number of batteries are required. However, since a lithium battery has a high driving voltage (3-4V class), it can be completed with fewer batteries, and thus there is an increasing expectation for practical use.

The lithium secondary battery can be used repeatedly by metal ions being inserted or intercalated between the negative electrode and the positive electrode. Conventional lithium secondary batteries can exhibit a high discharge voltage of 4 V class by using LiCoO ₂ as a positive electrode material, and have been put into practical use.

However, cobalt has a problem that it is difficult to ensure safety because of its scarce resources and high price. Therefore, an alternative material for the LiCoO ₂ positive electrode is required for practical use of large batteries. In recent years, lithium iron phosphate (LiFePO ₄ ) has attracted attention and has been put to practical use as a highly safe and inexpensive alternative material. The operating voltage of lithium iron phosphate is as high as about 3.5 V, which is an excellent positive electrode material from the viewpoint of safety, and has been studied as an electrode material for large batteries. However, since lithium iron phosphate has low conductivity, it needs to be carbon coated or nano-sized, and it is known that the production cost is high due to sintering under a special atmosphere.

  Among low-cost materials similar to iron, lithium cuprate has good conductivity and allows lithium ions to enter and exit, and is reported to be promising as a positive electrode material (Non-patent Document 1). The conductivity of copper oxide is about 10 times higher than that of iron, and since the synthesis is relatively simple, it is promising in terms of cost.

  However, lithium cuprate with a high theoretical capacity (489 mAh / g) shows a similar high value (430 mAh / g), but the capacity after the second cycle is reduced to about half, and is practical. The capacity is small, and improvement of energy density is a problem.

Japanese Patent Laid-Open No. 10-247496

H. Arai, S. Okada, Y. Sakurai, J. Yamaki, Solid State Ionic 106 (1998) 45-53. N. Imanishi, K. Shizuka, T. Ikenishi, T. Matsumura, A. Hirano, Y. Takeda, Solid State Ionics 177 (2006) 1341-1346.

  Lithium cuprate, which is promising as a positive electrode material for low-cost lithium secondary batteries, has a practical capacity and low operating voltage compared to layered nickel-based and cobalt-based materials. ing. Therefore, it is required to improve the capacity and operating voltage of lithium cuprate.

The reason for the large irreversible capacity is that the lithium cuprate (Li ₂ CuO ₂ ) in the cycle temporarily changes to Li ₃ Cu ₂ O ₄ , which is a metastable structure. However, it is reported that a cycle with a stable capacity is impossible (Non-Patent Document 1). In order to reduce the irreversible capacity of lithium cuprate, a method of replacing a part of copper with nickel as a dopant has been reported for the purpose of preventing a change in crystal structure that occurs during charge and discharge (non-patent document). Reference 2). This is because nickel is generally stable as divalent and can be improved in capacity and cycle by substituting it with a copper site in lithium cuprate present as divalent. However, a rare metal raw material such as nickel has a problem that the amount of money is scarce and the price is high. On the other hand, not all transition metals similar to nickel can be substituted for the copper site of lithium cuprate.

  For example, iron, which is the cheapest material among transition metals, can be in the same divalent state as copper and nickel, but iron is easily oxidized to a trivalent or tetravalent state that is more stable depending on the environment. . When iron is doped into lithium cuprate using conventional synthesis methods, there is a problem that it exists as trivalent and cannot be successfully replaced with a copper site. Further, the oxidized iron reacts with lithium to produce spinel type lithium ferrate which is inactive as an electrode of a lithium ion secondary battery.

  In view of this, the present invention proposes a synthesis method in which a divalent stable element such as iron is stabilized and doped as a divalent valence similar to copper. Therefore, in order to solve the above-described conventional problems, the present invention aims to improve the discharge capacity and electrode potential of lithium cuprate, which is a lithium secondary battery positive electrode material that is safe and excellent in cycle stability. An object of the present invention is to provide an inexpensive material for improving the safety, energy density, or cycle characteristics of a secondary battery.

The present invention solves the above problems, and one embodiment of the present invention has a crystal structure belonging to the space group Immm, and has the chemical formula LiCu _1-x M _x O ₂ (M is a metal, 0 The present invention relates to a positive electrode material for a lithium secondary battery, which is lithium cuprate represented by .01 ≦ x ≦ 0.45). The metal M of the present invention is preferably a transition metal, and more preferably Ti, V, Cr, Mn, Fe, or Co. Among these, Ti, V or Fe is more preferable. In the present invention, the doping amount x of the metal M is preferably 0.05 ≦ x ≦ 0.45.

  Another aspect of the present invention is a method for producing the lithium secondary battery positive electrode material of the present invention, wherein lithium cuprate and metal M powder (M has a valence of 0) are used as raw materials. The present invention relates to a method for producing a positive electrode material for a lithium secondary battery, wherein heating is performed at a temperature of 600 ° C. or higher for at least 3 hours in an oxygen atmosphere. Moreover, as a raw material of a manufacturing method using a lithium secondary battery positive electrode material, it is preferable to mix and use a copper oxide powder, a metal M powder (M has a valence of 0), and a lithium compound.

  Furthermore, another aspect of the present invention includes a positive electrode containing the lithium secondary battery positive electrode material of the present invention as a positive electrode active material, a negative electrode containing a negative electrode material capable of lithium insertion / extraction, and a positive electrode and a negative electrode. The present invention relates to a lithium secondary battery having a lithium ion conductive electrolyte disposed therebetween.

  The present invention improves the discharge capacity and electrode potential of lithium cuprate, which is a positive electrode material for lithium secondary batteries with high safety and excellent cycle stability, and improves the safety, energy density, or cycle characteristics of lithium secondary batteries. An inexpensive material for improvement can be provided.

It is battery sectional drawing showing the structure of the test cell of this invention. It is a figure which shows the XRD pattern of Example 1 sample of this invention. It is a charging / discharging curve of the 10th cycle of the sample of Example 1 of this invention and the comparative example 1. FIG.

  Below, the positive electrode material for lithium secondary batteries by this invention and its manufacturing method are demonstrated.

(1) Positive electrode material for lithium secondary battery The positive electrode material for lithium secondary battery of the present invention has a crystal structure belonging to the space group Immm, and has the chemical formula LiCu _1-x M _x O ₂ (M is a metal, 0.01 ≦ x ≦ 0.45), which is lithium cuprate.

The composition of the formula LiCu _1-x M _x O ₂ is synthesized by doping lithium cuprate with a metal having a valence greater than divalent and having stability, preferably a transition metal. The metal M is preferably a transition metal, and specific examples include Ti, V, Cr, Mn, Fe, and Co. Of these metals, Ti, V or Fe is more preferable.

The doping amount x of the metal M in the chemical formula LiCu _1-x M _x O ₂ is 0.01 ≦ x ≦ 0.45, preferably 0.05 ≦ x ≦ 0.45, and 0.1 ≦ x ≦ 0. 40 is more preferable, and 0.1 ≦ x ≦ 0.35 is particularly preferable. This is because if the doping amount x of the metal M is too small, the effect of the doped transition metal cannot be obtained, and if it is too large, the discharge capacity of lithium cuprate becomes too small.

The positive electrode material for a lithium secondary battery of the present invention is also characterized by having a crystal structure belonging to the space group Immm. As described in the description of the manufacturing method, this crystal structure is obtained by mixing copper oxide powder, metal M powder (M has a valence of 0), and a lithium compound, and heating the mixture to lithium cuprate. A positive electrode material containing lithium cuprate having a structure of LiCu _1-x M _x O ₂ doped with metal M and having a crystal structure belonging to the space group Immm can be obtained.

  In the present invention, any crystallinity may be used as long as it has a crystal structure belonging to the space group Immm. Specifically, it can be determined whether or not it has a crystal structure belonging to the space group Immm by comparing with a pattern of a lithium cuprate having a known Immm structure (PDF01-079-1975).

(2) Method for producing positive electrode material for lithium secondary battery The positive electrode material for lithium secondary battery of the present invention can be produced by the following method.

  First, the positive electrode material for a lithium secondary battery according to the present invention uses at least 3 at a temperature of 600 ° C. or higher in an oxygen atmosphere using lithium cuprate and metal M powder (M has a valence of 0) as raw materials. By heating for a period of time, it can be manufactured by doping the metal M into lithium cuprate.

  The manufacturing method of the present invention uses metal M powder in which the valence of M is 0 in order to dope the metal M so that it is replaced with the copper site of lithium cuprate in the divalent state. It is a feature. To dope the lithium cuprate, use a metal, preferably a transition metal, and powder of Ti, V, Cr, Mn, Fe or Co (the valence of these metals is 0) Is preferred.

  As a raw material which comprises lithium cuprate, the combination of the powder of a copper oxide and a lithium compound can be mentioned, for example. Specific examples of the copper oxide include, for example, cuprous oxide and cupric oxide, and specific examples of the lithium compound include a lithium compound having a melting point of 500 ° C. or higher. Lithium carbonate, lithium chloride, lithium fluoride, lithium phosphate, lithium sulfate, lithium hydroxide, and among these, it is preferable to use lithium hydroxide. In order to obtain lithium cuprate having the aimed composition, it is desirable to add more lithium compound than the stoichiometric ratio.

In addition, according to the production method of the present invention, copper oxide powder, lithium compound, metal M powder (M has a valence of 0), for example, Ti powder, V powder, Cr powder, Mn powder, Fe powder Co powder is mixed and heated in an oxygen atmosphere at a temperature of 600 ° C. or higher for at least 3 hours, thereby having a crystal structure belonging to the space group Immm and having the chemical formula LiCu _1-x M _x O. ₂ (M is a metal, and a lithium cuprate-containing positive electrode material represented by 0.01 ≦ x ≦ 0.45) can be produced.

  As described above, the production method of the present invention is performed in an oxygen atmosphere. Moreover, although the manufacturing method of this invention is characterized by performing reaction at the temperature of 600 degreeC or more, it is preferable to carry out at 700 to 1000 degreeC, and it is more preferable to carry out at 800 to 900 degreeC. .

  The production method of the present invention is characterized in that the reaction is carried out for 3 hours or more, preferably 5 hours to 24 hours, more preferably 8 hours to 15 hours.

  Other conditions can manufacture the positive electrode material for lithium secondary batteries containing lithium cuprate of the present invention by using a conventionally known method.

(3) Manufacture of Battery Positive Electrode The lithium cuprate-containing positive electrode material manufactured according to the present invention is formed into a pellet shape or a coated sheet shape as a positive electrode active material in the same manner as a conventional positive electrode material. A lithium secondary battery can be formed by combining the negative electrode material and a known organic electrolyte into a coin shape, a cylindrical shape, a square shape, a sheet shape, or the like.

  More specifically, in order to form a battery positive electrode using the lithium cuprate-containing positive electrode material of the present invention as a positive electrode active material, a mixture of the positive electrode material and a binder (polytetrafluoroethylene: PTFE or the like) is made of stainless steel or the like. Press molding on the support. Alternatively, a conductive agent (acetylene black or the like) is mixed to impart conductivity to the active material powder, and a binder is further added as necessary, and the mixture is put in a metal container, or on a support such as stainless steel. It is formed by means such as pressure forming, or dispersed in a solvent such as an organic solvent to form a slurry and apply it onto a metal substrate.

  Examples of the conductive agent include conductive carbon, and more specifically, carbon blacks such as acetylene black, ketjen black, and carbon black, activated carbons, and graphites. The conductive agent is preferably in the form of powder, is not particularly limited as long as it is inactive with respect to lithium cuprate and has a particle diameter suitable for ensuring sufficient conductivity between the lithium cuprate particles and the battery case. Generally, it is preferable from the viewpoint of conductivity that the surface of the lithium cuprate particles is in contact with the carbon particles. The carbon particles preferably have a size smaller than that of lithium cuprate.

  The binder is not particularly limited, and binders used in ordinary lithium ion secondary batteries such as polytetrafluoroethylene (PTFE), polyethylene, polypropylene, and polyvinylidene fluoride (PVDF) can be used. Moreover, it is preferable that the shape of a binder is a powder form.

(4) Lithium secondary battery using the lithium cuprate-containing positive electrode material of the present invention In a battery using the lithium cuprate-containing positive electrode material of the present invention as a positive electrode active material, lithium is reversibly inserted, desorbed, occluded, Lithium ions travel between the positive electrode and the negative electrode by having a negative electrode containing a substance that can be released and a substance that can move lithium ions to perform an electrochemical reaction with the positive electrode and the negative electrode as an electrolyte substance. It becomes a battery. For example, as the negative electrode active material, graphite, alloy-based lithium, tin, silicon, aluminum, or an oxide, lithium lithium titanate (Li ₅ Ti ₄ O ₁₂ ), and a nitride (Li _2.4 Co Conventionally known materials such as _0.4 N, Li _2.4 Fe _0.4 N) can be used.

  In the battery used for the positive electrode active material containing lithium cuprate of the present invention, as an electrolyte, for example, methoxyethane, diethoxyethane, 2-methyltetrahydrofuran, ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate, methyl formate, A non-aqueous electrolyte solvent in which a lithium salt is dissolved in an organic solvent such as dimethyl sulfoxide, acetonitrile, butyrolactone, dimethylformamide, dimethyl carbonate, diethyl carbonate, sulfolane, ethyl methyl carbonate or the like, or a solid electrolyte, a polymer electrolyte, and the organic solvent supported The polymer electrolyte etc. which were made to use can be used.

  The nonaqueous electrolytic solvent (liquid) is not particularly limited, and a nonaqueous electrolytic solution used for a normal lithium ion secondary battery can be used. Moreover, the porous film of the polypropylene or polyethylene currently used for the normal lithium ion secondary battery can also be used as a separator.

  Furthermore, various other publicly known materials can be used for other elements such as a structural material such as a battery case, and there is no particular limitation.

  Moreover, this can also be used as a secondary battery by repeatedly discharging and charging the battery.

(5) Performance Evaluation of Positive Electrode Material for Lithium Secondary Battery Next, the configuration of the test cell used for the performance evaluation of the positive electrode material for the lithium secondary battery of the present invention is based on the battery cross-sectional view shown in FIG. I will explain.

  1-1 is a negative electrode case, FIG. 1-2 is a negative electrode body made of metallic lithium, FIG. 1-3 is a gasket, FIG. 1-4 is a positive electrode body made of positive electrode material pellets, FIG. 1-5 is a positive electrode case, FIG. -6 shows a separator, and FIGS. 1-7 show non-aqueous electrolytes.

  A nickel mesh is welded to the inside of the negative electrode case (FIG. 1-1), and a negative electrode body (FIG. 1-2) obtained by punching a metal lithium sheet into a circle is pressure-bonded thereon. Next, a gasket (FIG. 1-3) is set to the outer peripheral part of a negative electrode case (FIG. 1-1).

  The positive electrode material pellet constituting the working electrode body (FIGS. 1-4) is composed of the lithium cuprate-containing positive electrode material of the present invention, a conductive agent (acetylene black) and a binder (polytetrafluoroethylene: PTFE), (positive electrode material: acetylene). (Black: PTFE = 70: 25: 5 composition weight ratio), and after mixing with a raking machine, the sheet was formed by roll pressing into a predetermined size (15 mm circular shape). . The prepared pellets were dried in vacuum and then placed on a working electrode case (FIG. 1-5) previously welded with a titanium mesh, further covered with a titanium mesh, and the titanium mesh and working electrode case (FIG. 1-5) were welded. The pellet was fixed by crimping the entire mesh later. A non-aqueous electrolyte (FIG. 1-7) and a separator (FIG. 1-6) are placed in the working electrode case to which the positive electrode material pellet is fixed, and a negative electrode case and a gasket are set thereon (FIG. 1-1). ) And finally the case was caulked to produce a test cell.

A charge / discharge test was conducted on the test cell thus fabricated under the conditions of a current density of 1 mA / cm ² and a voltage range of 0.5 to 3.5 V, and the results were evaluated.

  In addition, the test cell used for the performance evaluation of the positive electrode material for lithium secondary battery manufactured according to the present invention is shown as an example, and the present invention is not limited at all. Can be implemented.

  Examples of the positive electrode material for a lithium secondary battery and a battery using the positive electrode material according to the present invention will be described in detail below. In addition, this invention is not limited to the following Example, In the range which does not change the summary, it can change suitably and can implement.

Example 1
In Example 1, lithium hydroxide, copper oxide, and Fe powder were weighed and mixed so that the molar ratio was Li: Cu: Fe = 2: 0.9: 0.1, and 800 mg in an oxygen atmosphere. Li ₂ Cu _0.9 Fe _0.1 O ₂ was synthesized by heat treatment at 20 ° C. for 12 hours.

  The result of analyzing the crystal structure of the obtained sample with an X-ray diffractometer (XRD) is shown in FIG. Since this pattern coincided with the pattern of lithium cuprate having a known Immm structure shown in FIG. 2 (PDF01-079-1975), this sample was evaluated to have a crystal structure belonging to the space group Immm.

  Next, a coin cell (2320 size) using the sample prepared above as a positive electrode and metal lithium as a negative electrode was prepared, and the electrode characteristics were evaluated by the evaluation method described in the performance evaluation of (5) above.

  Specifically, a lithium cuprate-containing positive electrode material of the present invention, a conductive agent (acetylene black), and a binder (polytetrafluoroethylene: PTFE) (positive electrode material: acetylene black: PTFE = 70: 25: 5 composition weight ratio) In addition, after being pulverized and mixed with a rough machine, it was rolled into a sheet by a roll press until the thickness became 0.5 mm. The obtained sheet was punched into a circular shape having a diameter of 15 mm and vacuum-dried overnight to produce pellets.

  Next, a titanium mesh having a diameter of 15 mm was welded to the inside of the positive electrode case of the test cell, and the above pellets were lightly crimped on the mesh. Further, the top of the positive electrode material pellet was covered with a titanium mesh having a diameter of 17 mm, and the titanium mesh was welded to the positive electrode case, and then the pellet containing lithium cuprate was fixed to the positive electrode case by further pressing. On the other hand, a nickel mesh was welded to the inside of the negative electrode case, a metal lithium sheet having a diameter of 17 mm was pressure-bonded thereon, and a gasket was set on the outer edge of the negative electrode case.

Next, about 2 mL of non-aqueous electrolyte (1 mol / L LiPF ₆ / EC + DMC (EC: ethylene carbonate, DMC: dimethyl carbonate)) is poured into the positive electrode case on which the positive electrode material pellets are fixed, and a polyethylene separator is immersed in the gasket. A test cell was produced by covering the negative electrode case set with the top of the positive electrode case and caulking the whole.
As a result of conducting a charge / discharge test on the test cell manufactured as described above under the conditions of a current density of 1 mA / cm ² and a voltage range of 0.5 to 3.5 V, the 10th charge / discharge curve is shown in FIG. Show. Compared with the sample of lithium cuprate (Comparative Example 1) not subjected to metal doping, the discharge capacity was improved.

  Table 1 shows the initial discharge capacity and the discharge capacity at the 10th cycle. When the positive electrode material of Example 1 was used, when the initial discharge capacity was 150 mAh / g, a large discharge capacity of 145 mAh / g was maintained up to the 10th cycle.

(Example 2-6)
In Example 2, a sample was synthesized by the same method as in Example 1 except that Ti powder was used instead of iron powder as a raw material, and the crystal structure analysis and electrode characteristic evaluation of the obtained sample were performed. .

  In Example 3, it carried out similarly using V powder instead of iron powder. Further, Example 4 was performed in the same manner using Cr powder, Example 5 using Mn powder, and Example 6 using Co powder. As a result of analysis by XRD, the crystal structure of the sample obtained in Example 2-6 was all evaluated to have a crystal structure belonging to the space group Immm.

  Table 1 shows the initial discharge capacity and the discharge capacity at the 10th cycle. According to the results of the electrode characteristic evaluation, the sample of Example 2 had an initial discharge capacity of 139 mAh / g and was 127 mAh / g even at the 10th cycle. The sample of Example 3 had an initial discharge capacity of 152 mAh / g and was 147 mAh / g even at the 10th cycle. The sample of Example 4 had an initial discharge capacity of 146 mAh / g and was 129 mAh / g even at the 10th cycle. The sample of Example 5 had an initial discharge capacity of 149 mAh / g, and 131 mAh / g at the 10th cycle. The sample of Example 6 had an initial discharge capacity of 151 mAh / g, and a large discharge capacity of 140 mAh / g was maintained up to the 10th cycle even at the 10th cycle.

(Example 7)
In Example 7, Li ₂ Cu _0.9 Fe0. ₁ O ₂ powder was synthesized and subjected to X-ray crystal structure analysis and electrode characteristic evaluation. XRD analysis confirmed that it belonged to the Immm space group. As a result of the electrode characteristic evaluation, as shown in Table 2, the initial discharge capacity was 119 mAh / g, and a large discharge capacity of 86 mAh / g was maintained up to the 10th cycle even at the 10th cycle.

(Example 8-10)
In Example 8-10, the influence of the heat treatment time was examined. The heat treatment was performed for 3 hours in Example 8, 5 hours in Example 9, and 24 hours in Example 10 to synthesize Li ₂ Cu _0.9 Fe _0.1 O ₂ powder, and the obtained sample was analyzed by XRD. By analysis, it was confirmed to belong to the Immm space group.

  Table 3 shows the results of the initial discharge capacity and the discharge capacity at the 10th cycle for samples prepared under different heat treatment times. The sample of Example 8 had an initial discharge capacity of 125 mAh / g and was 111 mAh / g even at the 10th cycle. The sample of Example 9 had an initial discharge capacity of 123 mAh / g and was 90 mAh / g even at the 10th cycle. The sample of Example 10 had an initial discharge capacity of 121 mAh / g and maintained a large discharge capacity of 88 mAh / g up to the 10th cycle even at the 10th cycle.

(Examples 11-13)
In Examples 11-13, the influence of the doping concentration was examined. That is, in Example 11, the iron-doped lithium cuprate Li ₂ Cu _1-x Fe _x O ₂ (x =) under the same conditions as in Example 1 except that the iron doping amount was x = 0.01. Dope concentration) powder was synthesized under the same heat treatment conditions. In Example 12, the synthesis was performed under the same conditions as in Example 1 except that the doping amount of iron was x = 0.25, and in Example 13, the doping amount of iron was x = 0.35. The crystal structure of each of the obtained samples was analyzed by XRD, and it was confirmed that all belong to the Immm space group.

  Table 4 shows the initial discharge capacity and the discharge capacity at the 10th cycle for samples made of Fe with different dope concentrations. As a result of the electrode characteristic evaluation, the sample of Example 11 had an initial discharge capacity of 143 mAh / g and was 137 mAh / g even at the 10th cycle. The sample of Example 12 had an initial discharge capacity of 168 mAh / g and was 159 mAh / g even at the 10th cycle. The sample of Example 13 had an initial discharge capacity of 172 mAh / g, and a large discharge capacity of 168 mAh / g was maintained up to the 10th cycle even at the 10th cycle.

  In Examples 14-28, transition metals other than iron were used as dopants instead of iron, and the influence of the concentration of each dopant was examined.

  That is, in Examples 14-16, Ti was used instead of iron and it doped to lithium cuprate, and the influence was examined. Moreover, the influence of the doping concentration was examined for each dopant. Similarly, Examples 17-19 use V, Examples 20-22 use Cr, Examples 23-25 use Mn, Examples 26-28 use Co, and so on. The effect of doping with lithium cuprate was examined. For each dopant, the influence of the dopant concentration was examined.

(Examples 14-16) Ti-doped lithium cuprate / Li ₂ Cu _1-x Ti _x O ₂ (x = doping concentration) powder In Example 14, when Ti was used, the doping amount was x = 0 1. In Example 15, lithium cuprate doped with Ti was prepared so that x = 0.25 in Example 15 and x = 0.35 in Example 16. The crystal structure of each of the obtained samples was analyzed by XRD, and it was confirmed that all belong to the Immm space group.

  Table 5 shows the initial discharge capacity and the discharge capacity at the 10th cycle when Ti is doped at different concentrations. According to the results of the electrode characteristic evaluation, the sample of Example 14 had an initial discharge capacity of 139 mAh / g and 135 mAh / g even at the 10th cycle. The sample of Example 15 had an initial discharge capacity of 146 mAh / g and 139 mAh / g even at the 10th cycle. The sample of Example 16 maintained an initial discharge capacity of 141 mAh / g and a large discharge capacity of 135 mAh / g up to the 10th cycle even at the 10th cycle.

Examples 17-19 V-doped lithium cuprate / Li ₂ Cu _1-x V _x O ₂ (x = dope concentration) powder In Example 17, when V is used, the doping amount is x = 0 0.1, lithium cuprate doped with V was synthesized so that x = 0.25 in Example 18 and x = 0.35 in Example 19. The crystal structure of each of the obtained samples was analyzed by XRD, and it was confirmed that all belong to the Immm space group.

  Table 6 shows the initial discharge capacity and the discharge capacity at the 10th cycle when V is doped at different concentrations. According to the results of the electrode characteristic evaluation, the sample of Example 17 had an initial discharge capacity of 152 mAh / g and was 147 mAh / g even at the 10th cycle. The sample of Example 18 had an initial discharge capacity of 153 mAh / g and was 150 mAh / g even at the 10th cycle. The sample of Example 19 had an initial discharge capacity of 156 mAh / g, and a large discharge capacity of 151 mAh / g was maintained up to the 10th cycle even at the 10th cycle.

(Examples 20-22) Cr-doped lithium cuprate / Li ₂ Cu _1-x Cr _x O ₂ (x = dope concentration) powder In Example 20, when Cr is used, the doping amount is x = 0. 0.1, lithium cuprate doped with Cr was synthesized so that x = 0.25 in Example 21 and x = 0.35 in Example 22. The crystal structure of each of the obtained samples was analyzed by XRD, and it was confirmed that all belong to the Immm space group.

  Table 7 shows the initial discharge capacity and the discharge capacity at the 10th cycle when Cr is doped at different concentrations. According to the results of the electrode characteristic evaluation, the sample of Example 20 had an initial discharge capacity of 144 mAh / g, and was 128 mAh / g even at the 10th cycle. The sample of Example 21 had an initial discharge capacity of 151 mAh / g and was 136 mAh / g even at the 10th cycle. The sample of Example 22 had an initial discharge capacity of 152 mAh / g, and a large discharge capacity of 141 mAh / g was maintained up to the 10th cycle even at the 10th cycle.

(Example 23-25) Mn-doped lithium cuprate / Li ₂ Cu _1-x Mn _x O ₂ (x = doping concentration) powder In Example 23, when Mn was used, the doping amount was x = 0 1. In Example 24, lithium cuprate doped with Mn was synthesized so that x = 0.25 in Example 24 and x = 0.35 in Example 25. The crystal structure of each of the obtained samples was analyzed by XRD, and it was confirmed that all belong to the Immm space group.

  Table 8 shows the initial discharge capacity and the discharge capacity at the 10th cycle when Mn is doped at different concentrations. According to the results of the electrode characteristic evaluation, the sample of Example 23 had an initial discharge capacity of 136 mAh / g and 121 mAh / g even at the 10th cycle. The sample of Example 24 had an initial discharge capacity of 146 mAh / g and was 140 mAh / g even at the 10th cycle. The sample of Example 25 had an initial discharge capacity of 151 mAh / g, and a large discharge capacity of 141 mAh / g was maintained up to the 10th cycle even at the 10th cycle.

(Examples 26-28) Co-doped lithium cuprate / Li ₂ Cu _1-x Co _x O ₂ (x = doping concentration) powder In Example 26, when Co is used, the doping amount is x = 0. 0.1, Co-doped lithium cuprate was synthesized so that x = 0.25 in Example 27 and x = 0.35 in Example 28. The crystal structure of each of the obtained samples was analyzed by XRD, and it was confirmed that all belong to the Immm space group.

  Table 9 shows the initial discharge capacity and the discharge capacity at the 10th cycle when Co is doped at different concentrations. According to the results of the electrode characteristic evaluation, the sample of Example 26 had an initial discharge capacity of 139 mAh / g and was 127 mAh / g even at the 10th cycle. The sample of Example 27 had an initial discharge capacity of 144 mAh / g, and was 137 mAh / g even at the 10th cycle. The sample of Example 28 had an initial discharge capacity of 170 mAh / g, and a large discharge capacity of 134 mAh / g was maintained up to the 10th cycle even at the 10th cycle.

(Comparative Example 1)
In Comparative Example 1, lithium hydroxide and copper oxide were weighed and mixed so that the molar ratio was Li: Cu = 2: 1, and heated in an oxygen atmosphere at 800 ° C. for 12 hours. Li ₂ CuO ₂ was synthesized.

  As a result of analyzing the crystal structure of the obtained sample by XRD, it was confirmed that this sample had a crystal structure belonging to the space group Immm.

Next, a coin cell (2320 size) using the sample prepared above as a positive electrode and metallic lithium as a negative electrode was prepared, and the electrode characteristics were evaluated. Compared to a sample of lithium cuprate (Example 1) which was subjected to a charge / discharge test under the conditions of a current density of 1 mA / cm ² and a voltage range of 0.5 to 3.5 V, the discharge capacity is small. The sample material of Comparative Example 1 shows the initial discharge capacity and the discharge capacity at the 10th cycle. The initial discharge capacity was 125 mAh / g, and the 10th cycle was 110 mAh / g (Table 11).

(Comparative Example 2-7)
In Comparative Example 2-7, as the raw material used in Example 1, a metal raw material in an oxide powder state was used instead of the metal powder. A sample was synthesized in the same manner as in Example 1 except that TiO was used in Comparative Example 3, VO was used in Comparative Example 4, CrO was used in Comparative Example 5, MnO was used in Comparative Example 6, and CoO was used in Comparative Example 7. The crystal structure of the obtained sample was analyzed and the electrode characteristics were evaluated.

  As a result of XRD analysis, the crystal structure of the obtained sample was a mixed phase having impurities although a crystal structure belonging to the space group Immm exists as a main layer.

  Table 10 shows the initial discharge capacity and the discharge capacity at the 10th cycle. According to the results of the electrode characteristic evaluation, the sample material of Comparative Example 2 had an initial discharge capacity of 90 mAh / g and 63 mAh / g at the 10th cycle. The sample material of Comparative Example 3 had an initial discharge capacity of 83 mAh / g and 78 mAh / g at the 10th cycle. The sample material of Comparative Example 4 had an initial discharge capacity of 81 mAh / g and 73 mAh / g at the 10th cycle. The sample material of Comparative Example 5 had an initial discharge capacity of 88 mAh / g and 70 mAh / g in the 10th cycle. The sample material of Comparative Example 6 had an initial discharge capacity of 75 mAh / g and 55 mAh / g at the 10th cycle. The sample material of Comparative Example 7 had an initial discharge capacity of 108 mAh / g and 88 mAh / g in the 10th cycle.

(Comparative Example 8-11)
In Comparative Example 8-11, the influence of the synthesis atmosphere was examined. That is, as in Example 1, iron-doped lithium cuprate was synthesized so that the doping amount was x = 0.1. In Comparative Example 8, 800 ° C. in a nitrogen atmosphere instead of an oxygen atmosphere. The synthesis was performed in 12 hours. In Comparative Example 9, the synthesis was performed in Ar gas, in Comparative Example 10 in the air, and in Comparative Example 11 in 5% H ₂ —N ₂ gas.

Samples treated in 5% H ₂ —N ₂ gas produced an alloy, and therefore, data acquisition by XRD and electrochemical property evaluation were not performed. For other samples, the results of analysis by XRD are summarized in FIG. Although all of the crystal structure belonging to the space group Immm exists as the main layer, it was a mixed phase having impurities. For comparison, a sample synthesized in the oxygen atmosphere of Example 1 was similarly shown. It was found that samples synthesized in an oxygen atmosphere use high crystallinity.

  Table 11 shows the initial discharge capacity and the discharge capacity at the 10th cycle. According to the results of the electrode characteristic evaluation, the sample material of Comparative Example 8 had an initial discharge capacity of 120 mAh / g, and 97 mAh / g at the 10th cycle. The sample material of Comparative Example 9 had an initial discharge capacity of 100 mAh / g and 32 mAh / g at the 10th cycle. The sample material of Comparative Example 10 had an initial discharge capacity of 105 mAh / g and 40 mAh / g at the 10th cycle. In any of the comparative examples, the value was low as compared with the heat treatment in an oxygen atmosphere.

(Comparative Example 12)
In Comparative Example 12, iron powder was used as a raw material, and iron-doped lithium cuprate was synthesized so that the dope amount was x = 0.1. The heat treatment was performed at 400 ° C., lower than that in Example 1, in an oxygen atmosphere for 12 hours.

  The evaluation result by XRD confirmed the peak of a small amount of copper oxide raw material. Since the heat treatment was performed at a low temperature, a part of the copper oxide having a high melting point was unreacted and existed as an impurity.

  The electrochemical characteristics of the synthesized samples were similarly evaluated, and the results are shown as the heat treatment temperature effect in Table 2. The initial discharge capacity was 62 mAh / g, and the discharge capacity at the 10th cycle was a low value of 37 mAh / g. Moreover, the capacity decrease occurred more rapidly than the 15th cycle.

(Comparative Example 13)
In Comparative Example 13, iron powder was used as a raw material, and iron-doped lithium cuprate was synthesized so that the dope amount was x = 0.1. For the synthesis, heat treatment was performed at 800 ° C. in an oxygen atmosphere for 1 hour, shorter than that of Example 1.

  The evaluation result by XRD confirmed the peak of a small amount of copper oxide raw material. Since the heat treatment was performed at a low temperature, a part of the copper oxide having a high melting point was unreacted and existed as an impurity. The electrochemical properties of the synthesized samples were similarly evaluated. As a result, as shown in the summary of the time effect of the heat treatment in Table 3, the initial discharge capacity was 61 mAh / g, and the discharge capacity at the 10th cycle was a low value of 38 mAh / g. Further, a sudden decrease in capacity occurred after the 14th cycle.

(Comparative Example 14-19)
In Comparative Examples 14-19, lithium cuprate was synthesized under the same conditions as in Example 1 except that the doping amount was reduced to x = 0.005. In Comparative Example 14, Fe was used as a metal dopant, Ti was used in Comparative Example 15, V was used in Comparative Example 16, Cr was used in Comparative Example 17, Mn was used in Comparative Example 18, and Co was used in Comparative Example 19. Doped lithium cuprate was synthesized. From the evaluation results by XRD, it was confirmed that a crystal structure in which all samples belong to the space group Immm exists as a main layer. The electrochemical characteristics of the synthesized samples were similarly evaluated, and as a result, the initial discharge capacity and the discharge capacity at the 10th cycle are shown as the electrochemical characteristics (Table 4-9). According to the results of the electrode characteristic evaluation, the sample material of Comparative Example 14 had an initial discharge capacity of 133 mAh / g and 123 mAh / g at the 10th cycle (Table 4). The sample material of Comparative Example 15 had an initial discharge capacity of 126 mAh / g and 118 mAh / g at the 10th cycle (Table 5). The sample material of Comparative Example 16 had an initial discharge capacity of 128 mAh / g and 113 mAh / g at the 10th cycle (Table 6). The sample material of Comparative Example 17 had an initial discharge capacity of 129 mAh / g and 119 mAh / g at the 10th cycle (Table 7). The sample material of Comparative Example 18 had an initial discharge capacity of 127 mAh / g and 114 mAh / g at the 10th cycle (Table 8). The sample material of Comparative Example 19 had an initial discharge capacity of 131 mAh / g and 119 mAh / g at the 10th cycle (Table 9).

(Comparative Example 20-25)
In Comparative Examples 20-25, metal-doped lithium cuprates were synthesized under the same conditions as in Example 1 with the doping amount increased to x = 0.5. In comparison 20, Fe is used as a metal dopant, in comparative example 21, Ti is synthesized, in comparative example 22, V is synthesized, in comparative example 23 is synthesized with Mn, and in comparative example 25 is synthesized lithium cuprate doped with Co. did.

  From the evaluation results by XRD, it was confirmed that a crystal structure in which all samples belong to the space group Immm exists as a main layer. The electrochemical characteristics of the synthesized samples were similarly evaluated, and as a result, the initial discharge capacity and the discharge capacity at the 10th cycle are shown as the electrochemical characteristics (Table 4-9). According to the results of the electrode characteristic evaluation, the sample material of Comparative Example 20 had an initial discharge capacity of 99 mAh / g and 86 mAh / g at the 10th cycle (Table 4). The sample material of Comparative Example 21 had an initial discharge capacity of 110 mAh / g and 89 mAh / g at the 10th cycle (Table 5). The sample material of Comparative Example 22 had an initial discharge capacity of 89 mAh / g and 79 mAh / g at the 10th cycle (Table 6). The sample material of Comparative Example 23 had an initial discharge capacity of 91 mAh / g and 77 mAh / g at the 10th cycle (Table 7). The sample material of Comparative Example 24 had an initial discharge capacity of 88 mAh / g and 67 mAh / g at the 10th cycle (Table 8). The sample material of Comparative Example 25 had an initial discharge capacity of 101 mAh / g and 98 mAh / g at the 10th cycle (Table 9).

  The present invention improves the discharge capacity and electrode potential of lithium cuprate, which is a positive electrode material for lithium secondary batteries with high safety and excellent cycle stability, and improves the safety, energy density, or cycle characteristics of lithium secondary batteries. Since it provides an inexpensive material for improvement, it has industrial applicability.

1: Negative electrode case 2: Metallic lithium 3: Gasket 4: Positive electrode active material pellet 5: Positive electrode case 6: Separator 7: Nonaqueous electrolyte

Claims (8)

It has a crystal structure belonging to the space group Immm, and is a lithium cuprate represented by the chemical formula LiCu _1-x M _x O ₂ (M is a metal, 0.01 ≦ x ≦ 0.45) A positive electrode material for a lithium secondary battery.   The positive electrode material for a lithium secondary battery according to claim 1, wherein the metal M is a transition metal.   3. The positive electrode material for a lithium secondary battery according to claim 1, wherein the metal is any one of Ti, V, Cr, Mn, Fe, and Co. 4.   3. The positive electrode material for a lithium secondary battery according to claim 1, wherein the metal is any one of Ti, V, Cr, and Fe.   5. The positive electrode material for a lithium secondary battery according to claim 1, wherein a doping amount x of the metal M is 0.05 ≦ x ≦ 0.45. It is a manufacturing method of the positive electrode material for lithium secondary batteries of any one of Claims 1-5,
Using lithium cuprate and metal M powder (M has a valence of 0) as raw materials,
A method for producing a positive electrode material for a lithium secondary battery, wherein the metal M is doped into lithium copper oxide by heating at a temperature of 600 ° C. or higher for at least 3 hours in an oxygen atmosphere. It is a manufacturing method of the positive electrode material for lithium secondary batteries of any one of Claims 1-5,
Mixing copper oxide powder, metal M powder (M valence is 0), and lithium compound,
A method for producing a positive electrode material for a lithium secondary battery, comprising heating at a temperature of 600 ° C. or higher for at least 3 hours in an oxygen atmosphere.   A positive electrode containing the positive electrode material for a lithium secondary battery according to any one of claims 1 to 5 as a positive electrode active material, a negative electrode containing a negative electrode material capable of inserting and removing lithium, and a positive electrode and a negative electrode A lithium secondary battery comprising a lithium ion conductive electrolyte disposed therebetween.

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