TWI437126B - Method for forming electrolytic lithium cobalt oxide coating - Google Patents

Method for forming electrolytic lithium cobalt oxide coating Download PDF

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TWI437126B
TWI437126B TW101124288A TW101124288A TWI437126B TW I437126 B TWI437126 B TW I437126B TW 101124288 A TW101124288 A TW 101124288A TW 101124288 A TW101124288 A TW 101124288A TW I437126 B TWI437126 B TW I437126B
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lithium
cobalt
coating
cobalt oxide
conductive substrate
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TW201402868A (en
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Shiow Kang Yen
Te Chin Chang
Wen Yu Hsieh
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Univ Nat Chunghsing
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

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Description

電解法製備鋰鈷氧化物塗層之方法Method for preparing lithium cobalt oxide coating by electrolysis

本發明係關於一種使用電解法製備鋰鈷氧化物塗層之製備方法。The present invention relates to a process for preparing a lithium cobalt oxide coating by electrolysis.

鋰離子二次電池具有高能量密度、操作電壓高、使用溫度範圍大、壽命長、無記憶效應等優點，且其製程技術成熟、外型輕薄、價格大眾化，對於日漸普及之可攜式電子產品，其應用可說是日益廣泛。由於鋰離子二次電池具有相當可觀的市場價值，其正極與負極材料被廣泛的研究。Lithium-ion secondary batteries have the advantages of high energy density, high operating voltage, large operating temperature range, long life, no memory effect, and the process technology is mature, the appearance is light, the price is popular, and the portable electronic products are becoming increasingly popular. Its application can be said to be increasingly widespread. Since lithium ion secondary batteries have considerable market value, their positive and negative electrode materials have been extensively studied.

目前應用於正極材料包括鋰鈷氧化物(LiCoO2 )、鋰錳氧化物(LiMnO2 ，LiMn2 O4 )、鋰鎳氧化物(LiNiO2 )、以及鋰鈷鎳氧化物(LiNi1-x Cox O2 ，0<x<1)，其中鋰鈷氧化物(LiCoO2 )具有高電容極良好的循環性，因此最被廣泛的使用。Currently applied to cathode materials include lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMnO 2 , LiMn 2 O 4 ), lithium nickel oxide (LiNiO 2 ), and lithium cobalt nickel oxide (LiNi 1-x Co). x O 2 , 0 < x < 1), in which lithium cobalt oxide (LiCoO 2 ) has a high capacitance and excellent cycleability, and thus is most widely used.

多數文獻指出，可利用溶膠凝膠法(sol-gel process)、熱噴霧法、以及自沉澱法蒐集LiCoO2 粉末，然而，由於製作出之LiCoO2 粉末顆粒較大，其粉末必須與黏著劑混合後成膜，再經由導電基材上沉積LiCoO2 塗層，如濺鍍法、電漿式化學沉積法、以及蒸鍍法，但由於沉積速度太慢，無法降低製造成本也不利於工業化的生產，有鑑於此，目前需發展出一種反應時間短且降低生產成本之製備方法。Most literatures indicate that LiCoO 2 powder can be collected by sol-gel process, thermal spray method, and self-precipitation method. However, since the LiCoO 2 powder particles are large, the powder must be mixed with the adhesive. After film formation, LiCoO 2 coating is deposited on the conductive substrate, such as sputtering, plasma chemical deposition, and evaporation, but the deposition rate is too slow to reduce the manufacturing cost and is not conducive to industrial production. In view of this, it is currently necessary to develop a preparation method which has a short reaction time and a low production cost.

本發明之主要目的係在提供一種使用電解法製備鋰鈷氧化物塗層之方法。The primary object of the present invention is to provide a method of preparing a lithium cobalt oxide coating using electrolysis.

為達成上述目的，本發明包括下列步驟：(A)提供一導電基材、一電解液、以及一供電單元，其中電解液包括鈷離子、以及鋰離子；(B)將導電基材置入電解液中，且導電基材係與供電單位電性連接；(C)通電使導電基材表面上產生一鋰鈷氧化物塗層；以及(D)熱處理鋰鈷氧化物塗層。To achieve the above object, the present invention comprises the following steps: (A) providing a conductive substrate, an electrolyte, and a power supply unit, wherein the electrolyte comprises cobalt ions and lithium ions; (B) placing the conductive substrate in the electrolysis In the liquid, the conductive substrate is electrically connected to the power supply unit; (C) energized to produce a lithium cobalt oxide coating on the surface of the conductive substrate; and (D) heat treated lithium cobalt oxide coating.

本發明之製備方法中，導電基材包括係選自：白金、不銹鋼、鈦基合金、鈷基合金、以及鎳基合金，但不受限。In the preparation method of the present invention, the conductive substrate comprises, but is not limited to, platinum, stainless steel, titanium-based alloy, cobalt-based alloy, and nickel-based alloy.

本發明之製備方法中之電解液，其中，鈷離子之濃度係為0.001 M到10 M，係由至少一選自：硝酸鈷溶液、硫酸鈷溶液、氫氧化鈷溶液、以及氯化鈷溶液所提供；鋰離子之濃度係為0.001 M到10 M，係由至少一選自：硝酸鋰溶液、氫氧化鋰溶液、以及氯化鋰溶液所提供。The electrolyte in the preparation method of the present invention, wherein the concentration of cobalt ions is 0.001 M to 10 M, and is at least one selected from the group consisting of cobalt nitrate solution, cobalt sulfate solution, cobalt hydroxide solution, and cobalt chloride solution. Provided; the concentration of lithium ions is from 0.001 M to 10 M, provided by at least one selected from the group consisting of lithium nitrate solution, lithium hydroxide solution, and lithium chloride solution.

本發明製備方法中供電單元，包括一操作單元、以及一參考電極，其中操作單元與導電基材電性連接；參考電極較佳為銀/氯化銀(Ag/AgCl)參考電極，進行電解法時，採用恆電位法，相對於參考電極，實施於供電單元之電位範圍，控制於-0.5~-3.0伏特為較佳，以及相對於參考電極，實施於供電單元之電流範圍，控制於0.5~100毫安培/平方公分為較佳。The power supply unit of the preparation method of the present invention comprises an operation unit and a reference electrode, wherein the operation unit is electrically connected to the conductive substrate; the reference electrode is preferably a silver/silver chloride (Ag/AgCl) reference electrode for electrolysis When the potentiostatic method is used, the potential range of the power supply unit is controlled relative to the reference electrode, preferably controlled from -0.5 to -3.0 volts, and the current range of the power supply unit relative to the reference electrode is controlled at 0.5~ 100 mA/cm 2 is preferred.

本發明製備方法中，於電解法後，將沉積於導電基材上之鋰鈷氧化物進行熱處理，其熱處理溫度範圍為200~800℃，較佳為250~600℃，且當熱處理溫度範圍為250~400℃，較佳為270~380℃時，可得結晶之LiCo2 O4 塗層；當熱處理 溫度範圍為400~600℃，較佳為450~550℃時，可得結晶之LiCoO2 塗層。In the preparation method of the present invention, after the electrolysis method, the lithium cobalt oxide deposited on the conductive substrate is subjected to heat treatment, and the heat treatment temperature ranges from 200 to 800 ° C, preferably from 250 to 600 ° C, and when the heat treatment temperature range is Crystalline LiCo 2 O 4 coating can be obtained at 250~400 ° C, preferably 270-380 ° C; when the heat treatment temperature ranges from 400 to 600 ° C, preferably from 450 to 550 ° C, crystalline LiCoO 2 can be obtained. coating.

本發明不必如同習知技術般，必須在控制良好的環境下操作，也減少了高真空鍍膜系統的絕對必要性，且以此方法所形成的LiCo2 O4 塗層，可在10分鐘之內獲得4微米(4μm)之厚度，與習知技術的每分鐘5奈米的速度相較下，相當具有改良、進步的效果，所以，這樣的方式不僅降低傳統濺鍍(PVD)、化學氣相沉積(CVD)所耗費的時間及設備、生產成本、更可大幅提升塗層技術的競爭力。The invention does not have to operate in a well-controlled environment as in the prior art, and also reduces the absolute necessity of a high vacuum coating system, and the LiCo 2 O 4 coating formed by this method can be within 10 minutes. Obtaining a thickness of 4 micrometers (4 μm), compared with the speed of 5 nanometers per minute of the prior art, is quite improved and improved, so that this method not only reduces the conventional sputtering (PVD), chemical vapor phase The time and equipment used for deposition (CVD), production costs, and the competitiveness of coating technology can be greatly improved.

經由本發明製備方法製作之鋰鈷氧化物塗層，可應用於鋰離子二次電池之正極材料，本發明之優點再於低成本、膜厚均勻、以及充電循環性佳。The lithium cobalt oxide coating produced by the preparation method of the present invention can be applied to a positive electrode material of a lithium ion secondary battery, and the advantages of the present invention are further low cost, uniform film thickness, and good charge cycle.

茲列舉以下四個實施例，以更加詳細說明本發明。The following four examples are given to illustrate the invention in more detail.

實施例一Embodiment 1

本實施例為本發明之電化學陰極極化實驗。將Ag/AgCl參考電極、導電基材及白金電極放進含Li離子之濃度為0.1M、以及Co離子之濃度為0.01 M之電解液中，以進行電化學陰極極化實驗，採用恆電位法，電壓範圍於-3.0V至0.5V間(相對於Ag/AgCl參考電極)，可以得到電位對電流的關係圖極化曲線，如圖1所示。This example is an electrochemical cathodic polarization experiment of the present invention. The Ag/AgCl reference electrode, the conductive substrate and the platinum electrode were placed in an electrolyte containing Li ions at a concentration of 0.1 M and a Co ion concentration of 0.01 M to conduct an electrochemical cathodic polarization experiment using a potentiostatic method. The voltage range is from -3.0V to 0.5V (relative to the Ag/AgCl reference electrode), and the potential versus current polarization curve can be obtained, as shown in Figure 1.

實施例二Embodiment 2

本實施例為本發明之電化學沉積鋰鈷氧化物塗層之方法：將參考電極、導電基材及白金電極放進含Li離子之濃 度為0.1M、以及Co離子之濃度為0.01 M之電解液中，由實施例一的極化測試實驗得知，電位範圍在-0.5~-3.0V之間可以得到非晶質的鋰鈷氧化物薄塗層，藉由電腦控制電位/電流值進行沉積鋰鈷氧化物塗層，經270℃~380℃的熱處理過後即可得到結晶的LiCo2 O4 塗層，其微觀表面型態如圖2所示。X光繞射圖譜如圖4所示。The present embodiment is a method for electrochemically depositing a lithium cobalt oxide coating according to the present invention: a reference electrode, a conductive substrate, and a platinum electrode are placed in an electrolysis solution having a Li ion concentration of 0.1 M and a Co ion concentration of 0.01 M. In the liquid, it is known from the polarization test of the first embodiment that a thin coating of amorphous lithium cobalt oxide can be obtained at a potential range of -0.5 to -3.0 V, and deposition is performed by a computer controlled potential/current value. The lithium cobalt oxide coating is subjected to heat treatment at 270 ° C to 380 ° C to obtain a crystallized LiCo 2 O 4 coating, and its microscopic surface morphology is shown in FIG. 2 . The X-ray diffraction pattern is shown in Figure 4.

實施例三Embodiment 3

本實施例為本發明之電化學沉積鋰鈷氧化物塗層之方法：將參考電極、導電基材及白金電極放進含Li離子之濃度為0.1M、以及Co離子之濃度為0.01 M之電解液中，由實施例一的極化測試實驗得知，電位範圍在-0.5~-3.0V之間可以得到非晶質的鋰鈷氧化物薄塗層，藉由電腦控制電位/電流值進行沉積鋰鈷氧化物塗層，經450℃~550℃的熱處理過後即可得到結晶的LiCoO2 塗層，其微觀表面型態如圖3所示。X光繞射圖譜如圖4所示。The present embodiment is a method for electrochemically depositing a lithium cobalt oxide coating according to the present invention: a reference electrode, a conductive substrate, and a platinum electrode are placed in an electrolysis solution having a Li ion concentration of 0.1 M and a Co ion concentration of 0.01 M. In the liquid, it is known from the polarization test of the first embodiment that a thin coating of amorphous lithium cobalt oxide can be obtained at a potential range of -0.5 to -3.0 V, and deposition is performed by a computer controlled potential/current value. The lithium cobalt oxide coating is subjected to heat treatment at 450 ° C to 550 ° C to obtain a crystallized LiCoO 2 coating, and its microscopic surface morphology is shown in FIG. The X-ray diffraction pattern is shown in Figure 4.

實施例四Embodiment 4

本實施例為本發明之電化學沉積LiCo2 O4 塗層應用於二次鋰離子電池單極測試(循環伏安測試)。將實例二所沉積的結晶LiCo2 O4 塗層，應用於鋰離子二次電池之正極材料，以循環伏安法進行單極的性能測試，以鋰金屬片作為正極及參考電極，電解液採用標準PC溶入1M LiClO4 之液態電解質，恆電位儀設定掃描速度0.5mV/sec，開路電位為起始電位，電壓範圍為3.0到4.0伏特，發現氧化及還原峰分別為3.75伏特及3.43伏特(相對於Li/Li+ )，如圖5所示。This example is an electrochemical deposition LiCo 2 O 4 coating of the present invention applied to a secondary lithium ion battery unipolar test (cyclic voltammetry test). The crystalline LiCo 2 O 4 coating deposited in Example 2 was applied to the positive electrode material of the lithium ion secondary battery, and the unipolar performance test was performed by cyclic voltammetry. The lithium metal piece was used as the positive electrode and the reference electrode, and the electrolyte was used. The standard PC was dissolved in 1M LiClO 4 liquid electrolyte. The potentiostat set the scanning speed to 0.5mV/sec, the open circuit potential was the starting potential, and the voltage range was 3.0 to 4.0 volts. The oxidation and reduction peaks were found to be 3.75 volts and 3.43 volts, respectively. Relative to Li/Li + ), as shown in FIG.

實施例五Embodiment 5

本實施例為本發明之沉積LiCo2 O4 塗層應用於二次鋰離子電池單極測試(充放電測試)。將實例二所沉積的結晶LiCo2 O4 塗層，應用於鋰離子二次電池之正極材料，以充放電進行單極的性能測試，以鋰金屬片作為負極，濃度1M的碳酸丙烯(propylene carbonate,PC)溶入過氯酸鋰(LiCl4 )作為電解質，以形成半電池，藉以用來測試鋰離子電池正極的效能，電容量越高代表此鋰離子電池的效能越好。而在進行充放電測試，充放電電壓範圍在3.2伏特~3.8伏特之間(相對於Li/Li+ )，電流密度為10μA/cm2 ，在充電、放電的過程中，隨著電位值其電容量的變化，並得到一第一次充放電電容量表現為77(mAh/g)，而一第三次充放電電容量則表現為75(mAh/g)，一第20次充放電電容量表現為71(mAh/g)。This example is a single-pole test (charge and discharge test) for a secondary lithium ion battery of the deposited LiCo 2 O 4 coating of the present invention. The crystalline LiCo 2 O 4 coating deposited in Example 2 was applied to the positive electrode material of the lithium ion secondary battery, and the monopolar performance test was performed by charging and discharging, using a lithium metal sheet as a negative electrode and a propylene carbonate having a concentration of 1 M. , PC) dissolves lithium perchlorate (LiCl 4 ) as an electrolyte to form a half-cell, which is used to test the performance of the positive electrode of the lithium-ion battery. The higher the capacity, the better the performance of the lithium-ion battery. In the charge and discharge test, the charge and discharge voltage ranges from 3.2 volts to 3.8 volts (relative to Li/Li + ), and the current density is 10 μA/cm 2 . During charging and discharging, the potential value is charged. The capacity change, and a first charge and discharge capacity is 77 (mAh / g), while a third charge and discharge capacity is 75 (mAh / g), a 20th charge and discharge capacity The performance is 71 (mAh / g).

實施例六Embodiment 6

本實施例為本發明之電化學沉積LiCoO2 塗層應用於二次鋰離子電池單極測試(循環伏安測試)。將實例三所沉積的結晶LiCoO2 塗層，應用於鋰離子二次電池之正極材料，以循環伏安法進行單極的性能測試，以鋰金屬片作為正極及參考電極，電解液採用標準PC溶入1M LiClO4 之液態電解質，恆電位儀設定掃描速度為0.5mV/sec，開路電位為起始電位，電壓範圍為3.0到4.2伏特，發現氧化及還原峰分別為3.98伏特及3.84伏特(相對於Li/Li+ )，如圖6所示。This example is an electrochemical deposition LiCoO 2 coating of the present invention applied to a secondary lithium ion battery unipolar test (cyclic voltammetry test). The crystalline LiCoO 2 coating deposited in Example 3 was applied to the positive electrode material of the lithium ion secondary battery, and the performance of the single pole was tested by cyclic voltammetry. The lithium metal piece was used as the positive electrode and the reference electrode, and the electrolyte was a standard PC. The liquid electrolyte dissolved in 1M LiClO 4 was set to a scanning potential of 0.5 mV/sec, the open circuit potential was the starting potential, and the voltage range was 3.0 to 4.2 volts. The oxidation and reduction peaks were found to be 3.98 volts and 3.84 volts, respectively. In Li/Li + ), as shown in Figure 6.

實施例七Example 7

本實施例為本發明之沉積LiCoO2 塗層應用於二次鋰離子電池單極測試(充放電測試)。將實例三所沉積的結晶LiCoO2 塗層，應用於鋰離子二次電池之正極材料，以充放電進行單極的性能測試，以鋰金屬片作為負極，濃度1M的碳酸丙烯(propylene carbonate,PC)溶入過氯酸鋰(LiCl4 )作為電解質，以形成半電池，藉以用來測試鋰離子電池正極的效能，電容量越高代表此鋰離子電池的效能越好。而在進行充放電測試，充放電電壓範圍在2.5伏特~4.2伏特之間(相對於Li/Li+ )，電流密度為10μA/cm2 ，在充電、放電的過程中，隨著電位值其電容量的變化，並得到一第一次充放電電容量為62(mAh/g)；而一第二次充放電電容量表現為53(mAh/g)，而一第三次充放電則表現為48(mAh/g)，一第20次充放電電容量表現為11(mAh/g)。This embodiment is a single-pole test (charge and discharge test) of a deposited LiCoO 2 coating of the present invention applied to a secondary lithium ion battery. The crystalline LiCoO 2 coating deposited in Example 3 was applied to the positive electrode material of the lithium ion secondary battery, and the performance of the monopole was tested by charging and discharging, using lithium metal sheet as the negative electrode and propylene carbonate (PC) having a concentration of 1 M. Lithium perchlorate (LiCl 4 ) is dissolved as an electrolyte to form a half-cell, which is used to test the performance of the positive electrode of the lithium ion battery. The higher the capacity, the better the performance of the lithium ion battery. In the charge and discharge test, the charge and discharge voltage ranges from 2.5 volts to 4.2 volts (relative to Li/Li + ), and the current density is 10 μA/cm 2 . During charging and discharging, the potential is charged with the potential value. The change in capacity, and a first charge and discharge capacity of 62 (mAh / g); and a second charge and discharge capacity of 53 (mAh / g), and a third charge and discharge performance 48 (mAh/g), a 20th charge and discharge capacity showed 11 (mAh / g).

上述實施例僅係為了方便說明而舉例而已，本發明所主張之權利範圍應以申請專利範圍所述為準，而非僅限於上述實施例。The above-mentioned embodiments are merely examples for the convenience of the description, and the scope of the claims should be based on the scope of the patent application, and not limited to the above embodiments.

圖1係本發明實施例一之電位對電流的關係圖極化曲線。1 is a polarization diagram of a relationship between a potential and a current in Embodiment 1 of the present invention.

圖2係本發明所合成之LiCo2 O4 塗層之微觀表面型態示意圖。Fig. 2 is a schematic view showing the microscopic surface state of the LiCo 2 O 4 coating synthesized by the present invention.

圖3係本發明所合成之LiCoO2 塗層之微觀表面型態示意圖。Fig. 3 is a schematic view showing the microscopic surface type of the LiCoO 2 coating synthesized by the present invention.

圖4係本發明所合成之鋰鈷氧化物塗層之X光繞射分析圖譜。Figure 4 is a X-ray diffraction analysis of the lithium cobalt oxide coating synthesized by the present invention.

圖5係本發明所合成之LiCo2 O4 塗層之循環伏安測試結果圖。Figure 5 is a graph showing the results of cyclic voltammetry of the LiCo 2 O 4 coating synthesized by the present invention.

圖6係本發明所合成之LiCoO2 塗層之循環伏安測試結果圖。Figure 6 is a graph showing the results of cyclic voltammetry of the LiCoO 2 coating synthesized by the present invention.

Claims (10)

一種使用電解法製備鋰鈷氧化物塗層之方法，包括下列步驟：(A)提供一導電基材、一電解液、以及一供電單元，其中該電解液包括鈷離子、以及鋰離子；(B)將該導電基材置入該電解液中，且該導電基材係與該供電單位電性連接；(C)通電使該導電基材表面上產生一鋰鈷氧化物塗層；以及(D)熱處理該鋰鈷氧化物塗層；其中，熱處理之溫度範圍係200~800℃，且當熱處理之溫度係250~400℃時，係得結晶之鋰鈷氧化物LiCo2 O4 塗層；當熱處理之溫度係400~600℃時，係得結晶之鋰鈷氧化物LiCoO2 塗層。A method for preparing a lithium cobalt oxide coating by electrolysis, comprising the steps of: (A) providing a conductive substrate, an electrolyte, and a power supply unit, wherein the electrolyte comprises cobalt ions, and lithium ions; Inserting the conductive substrate into the electrolyte, and the conductive substrate is electrically connected to the power supply unit; (C) energizing to produce a lithium cobalt oxide coating on the surface of the conductive substrate; and (D) Heat treating the lithium cobalt oxide coating; wherein the heat treatment temperature range is 200 to 800 ° C, and when the heat treatment temperature is 250 to 400 ° C, the crystalline lithium cobalt oxide LiCo 2 O 4 coating is obtained; When the temperature of the heat treatment is 400 to 600 ° C, a crystalline lithium cobalt oxide LiCoO 2 coating is obtained. 如申請專利範圍第1項所述之方法，其中該導電基材包括係選自：白金、不銹鋼、鈦基合金、鈷基合金、以及鎳基合金。 The method of claim 1, wherein the electrically conductive substrate comprises a layer selected from the group consisting of platinum, stainless steel, titanium based alloys, cobalt based alloys, and nickel based alloys. 如申請專利範圍第1項所述之方法，其中該鈷離子之濃度係為0.001M到10M。 The method of claim 1, wherein the concentration of the cobalt ion is from 0.001 M to 10 M. 如申請專利範圍第1項所述之方法，其中該鋰離子之濃度係為0.001M到10M。 The method of claim 1, wherein the lithium ion concentration is from 0.001 M to 10 M. 如申請專利範圍第1項所述之方法，其中該鈷離子由至少一選自硝酸鈷溶液、硫酸鈷溶液、氫氧化鈷溶液、以及氯化鈷溶液所提供。 The method of claim 1, wherein the cobalt ion is provided by at least one selected from the group consisting of a cobalt nitrate solution, a cobalt sulfate solution, a cobalt hydroxide solution, and a cobalt chloride solution. 如申請專利範圍第1項所述之方法，其中該鋰離子由至少一選自硝酸鋰溶液、氫氧化鋰溶液、以及氯化鋰溶液所提供。 The method of claim 1, wherein the lithium ion is provided by at least one selected from the group consisting of a lithium nitrate solution, a lithium hydroxide solution, and a lithium chloride solution. 如申請專利範圍第1項所述之方法，其中該供電單元包括一參考電極。 The method of claim 1, wherein the power supply unit comprises a reference electrode. 如申請專利範圍第7項所述之方法，其中相對於該參考電極，實施於該供電單位一電位範圍為-0.5~-3.0伏特。 The method of claim 7, wherein a potential range of the power supply unit is -0.5 to -3.0 volts relative to the reference electrode. 如申請專利範圍第7項所述之方法，其中相對於該參考電極，實施於該供電單位一電流範圍為0.5~100毫安培/平方公分。 The method of claim 7, wherein a current range of the power supply unit is 0.5 to 100 mA/cm 2 relative to the reference electrode. 如申請專利範圍第1項所述之製備方法，其製備出LiCo2 O4 以及LiCoO2 之塗層係作為鋰離子二次電池之正極材料使用。The preparation method according to the first aspect of the invention, wherein the coating of LiCo 2 O 4 and LiCoO 2 is used as a positive electrode material of a lithium ion secondary battery.
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