TW201222917A - Application method of lithium ion battery modifier, separator of lithium ion battery, and battery - Google Patents

Abstract

The invention relates to an application method of lithium ion battery modifier. In the method, a porous membrane used for separator of lithium ion battery and the modifier are provided. The modifier includes a liquid mixture of a phosphorus source having phosphate anion, a trivalent aluminum source and a metallic oxide. The modifier is coated on the surface of the porous membrane to form a coating layer. The porous membrane with the coating layer is dried to form a modifier layer on the surface of the porous membrane. The invention also relates to a separator of lithium ion battery prepared by the method above. The separator is applied to the lithium ion battery to increase the thermal stability and safety of the lithium ion battery.

Description

201222917 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a method for using a ionic battery modifier in a lithium ion battery, and a lithium ion battery separator and a lithium ion battery including the separator Technology·] [0002] At present, with the rapid development of electric vehicles and portable electronic devices such as mobile phones, digital cameras and notebook computers, the demand for high-power, high-energy density batteries is increasing. Lithium-ion batteries are the batteries with the highest voltage and highest energy density among the batteries that have been put to practical use so far, and have good development prospects. [0003] A lithium ion battery is mainly composed of an electrode, a separator, and an electrolyte. Diaphragm is an important component of lithium-ion batteries, which plays a role in preventing short-circuiting of electrodes and providing ion transmission channels during charge and discharge. Its performance directly affects the capacity, cycle performance and safety performance of lithium-ion batteries. characteristic. :: [0004] With the development of technology, more and more electronic devices require lithium-ion batteries to have a larger amount of grain, but the increase in the amount of grain will increase the amount of heat generated by the charge and discharge of the ion battery. This causes serious safety problems. The single-layer or multi-layer polymer porous film conventionally used as a separator causes melting under heat, which easily causes a short circuit between the electrodes, and even causes the lithium ion battery to burn or explode, which limits the application of the lithium ion battery. 099140716 In order to solve the above problems, in the prior art, the surface of the diaphragm is usually coated with an inorganic ceramic material such as oxidized in order to "break the diaphragm during charging and discharging or puncture form number A0101 page 4 / 40 pages 099207087-! [0005] 201222917 [0006] Ο [0008] [0009] 099140716 or the like caused by short circuit or self-discharge of the battery. Chinese Patent No. ZL03820566.1 discloses a separator having a plurality of porous inorganic insulating coatings. In the case of overheating of a lithium ion battery, the inorganic electrically insulating coating can prevent the electrode even if the polymer matrix of the separator melts. A short circuit between them improves the safety performance of the lithium ion battery. However, since alumina is a poorly soluble substance, the uniformity of coating is unsuitable for control, so that the thermal stability of the separator is affected. SUMMARY OF THE INVENTION In view of the above, it is necessary to provide a lithium ion battery modifier in a lithium ion battery to obtain a lithium ion battery separator having good thermal stability and a lithium ion battery having high safety. A method for using a lithium ion battery modifier, comprising the steps of: providing a porous film for a lithium ion battery separator and a lithium ion battery modifier, the modifier comprising a phosphate source containing phosphoric acid, a source of trivalent aluminum, and Mixing a metal oxide in a liquid phase solvent; applying a modifier to the surface of the porous film to form a coating layer, and drying the porous film coated with the modifier to form a surface on the porous film Layer of agent. A lithium ion battery separator comprising a porous membrane and a modifier layer disposed on the surface of the porous membrane, the modifier layer being in a liquid phase by using a phosphate-containing phosphorus source, a trivalent aluminum source, and a metal oxide After mixing in a solvent, coating on the surface of the porous film to form a coating layer, and drying the coating layer to form a lithium ion battery, including a positive electrode sheet, a negative electrode sheet, a separator, a non-aqueous electrolyte, and an external package structure. Wherein, the separator is the above lithium ion battery separator. Form No. 1010101 Page 5 of 40 0992070874-0 201222917 [0010] [0014] [0014] 099140716 Compared to the prior art, the present invention applies the lithium ion battery modifier to The porous membrane surface is used to test an ion battery separator. Since the modifier is a -clear solution, it is easy to form a uniform continuous and thinner layer on the surface of the surface, thereby improving the thermal stability of the separator and the sub-cell including the separator. Security performance. [Embodiment] Hereinafter, a timing method of a lithium ion battery modifier, a nano battery separator, and an ion battery of a lithium ion battery modifier according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. Since the lithium ion battery separator contains the component of the lithium ion battery modifier, the lithium ion battery modifier and the method of using the same will be described below. (I) Chain Ion Battery Modifier and Preparation Method Thereof First, a lithium ion battery modifier is provided in the embodiment of the present invention, and the modifier includes a sulphate-containing phosphorus source, a trivalent aluminum source, and a metal oxide. Mixing in a liquid phase solvent. The phosphate may be a light or a mixture of orthophosphate (PO 3 -), phosphonium dihydrogen (9), and 4 i 4 monohydrogen phosphate (HP 〇 42_). Wherein, the PO 3 -containing phosphorus source may be one or more of phosphoric acid (Η, ΡΟ J, triammonium phosphate ((ΝΗ4) 3Ρ〇4) and phosphoric acid (Α1Ρ〇4); The phosphorus source of ?0/ may be one or more of ammonium dihydrogen phosphate (ΝΗ4Η2Ρ〇4) and dihydrogen phosphate (Α1(Η2Ρ〇4)3); the phosphorus source containing ΗΡ〇42_ may be One or more of the monohydrogen phosphate ((ΝΗ4)2ΗΡ〇4) and the monohydrogen phosphate (Α12(ΗΡ〇4)3). The trivalent source may be aluminum hydroxide (Α1(0Η\), Alumina (A1Q0Q), aluminum phosphate U1P04), bismuth bisphosphonate (Α1(Η2Ρ〇4)3), and nitric acid phosphate (Α12(ΗΡ〇4)3) Form No. A0101 Page 6 One or more of a total of 40 pages 0992070874-0 201222917. The phosphate-containing phosphorus source and the trivalent aluminum source may be one of Α1Ρ〇4, Α1(Η2Ρ〇4)3, and Α12(ΗΡ04)3 at the same time. Or several. The metal oxides include chromium trioxide (Cr〇), zinc oxide (ΖηΟ) υ, copper oxide (CuO), magnesium oxide (Mg〇), zirconium dioxide (Zr〇2), molybdenum trioxide ( Mo〇3), vanadium pentoxide (v 〇), pentoxide One or more of sharp (Nb 〇) and pentoxide groups (Ta2 〇 5). [0015] The modifier is a clear solution having a certain viscosity. Water or N-methylpyrrolidone (NMP), etc., the molar ratio of the phosphorus source, the trivalent aluminum source, and the metal oxide is preferably (Al + M) : P = 1: 2. 5 to 1: 4. Al, bismuth and P are respectively the aluminum element in the aluminum source, the metal element in the metal halide and the number of moles of the phosphorus element in the phosphorus source. More preferably, the ratio is (Al + M) : P = 1:2. 5 to 1. When the metal oxide is Cr〇3, the modifier is a red clear solution. It is understood that in order to facilitate coating to form a thin and uniform coating, a lower concentration can be prepared. a modifier, or the modifier is diluted to a smaller concentration at the time of use, the total mass of the phosphate of the phosphorus source, the aluminum element of the trivalent aluminum source, and the metal element of the subsidiary oxide The bulk density of the total volume of the modifier is preferably from 0.02 g/ml to 0.08 g/ml. The modifier can be uniformly applied to the surface of the lithium ion battery current collector or the electrode sheet. The reaction occurs after heat (greater than 10 〇 ° C), and the composition of the heat-generating product is one of AlxMyP〇4 and AlxMy(P〇3)3 or a mixture of the two substances; wherein the valence of lanthanum is k, Μ It is a mixture of one or more of Cr, Zn, Cu, Mg, Zr, Mo, V, Nb, and Ta; 〇 < χ <1 ' 0<y<l and 3x + ky = 3. Preferably, the μ is Cr, k = 3, the composition of the heat-generating product is AlxCrl xP〇, and Al Cr (PO ) is x4 xl~*x 3 3 099140716 Form No. A0101 Page 7 / Total 40 Page 0992070874 -0 201222917 of the species or a mixture of the two. [0018] [0020] [0021] The lithium ion battery modifier can be prepared by the following method, including the following steps: Step one, providing a phosphate source containing phosphoric acid, a source of trivalent aluminum And the metal oxide 'and the second step, mixing the phosphorus source, the aluminum source and the metal oxide in a liquid phase solvent to form a clear solution. The above clear solution is the lithium ion battery modifier of the embodiment of the present invention. In the above step 1, the sulphate may be one or more of orthophosphate (p〇43-), dihydrogen dihydrogenate (h2p〇4-) and monohydrogen phosphate (HP〇42-). the mix of. Wherein, the phosphorus source may be one or more of phosphoric acid PO) 4 3 4y , triammonium phosphate ((Nh4)3p〇4) and phosphoric acid (aip〇4); the phosphorus containing LP0/ The source may be one or more of ammonium dihydrogen phosphate (ΝΗ Η P0 ) ^ 4 4 2 4 and aluminum dihydrogen phosphate (Α1(Η2Ρ04) 3); the phosphorus source containing ΗΡ〇42_ may be phosphoric acid One or more of ammonium hydrogen hydrochloride (Pg) 2HP 〇 4) and monohydrogen phosphate (A12 (HP 〇 4) 3). The trivalent source may be aluminum hydroxide (Al(〇H) J, alumina (AIqOO, aluminum phosphate (A1P0), 3^6 4 dihydrogen phosphate (Α1(Η2Ρ〇4)3)) and monohydrogen phosphate One or more of Α12(ΗΡ〇4)3. Preferably, the total mass of the phosphate of the phosphorus source, the aluminum element of the trivalent aluminum source, and the metal element of the metal oxide accounts for The bulk density of the total volume of the modifier is 〇. 〇2g/ral to 0.08g/ml. It is understood that the phosphate source containing phosphoric acid and the source of the trivalent aluminum can be simultaneously aip 〇 4, ai (h2p 〇 4 One or more of 3 and ai2(hp〇4) 3. The metal oxide includes chromium trioxide (Cr03), zinc oxide (Zn0), oxygen 099140716 Form No. A0101 Page 8 of 40 0992070874-0 201222917 Copper (CU〇), yttrium oxide, money (Mg0), zirconium dioxide (ZrO), molybdenum trioxide (M0\), pentoxide-4 h 2 9 4,, _ vanadium (V2〇5), The pentoxide oxide (Nb2〇5) and the pentoxide oxide (TaQ〇) are in the form of one or more of H 2 5 Y. In the embodiment of the present invention, 34 is used as the source, and the concentration of Η3Ρ(\ Preferably 6G% to 90%; mining (〇H)3 private end as a place A source of aluminum; using CrO powder as the metal oxide. 3 ^ [0022] The liquid phase solvent may be water or Ρ Ρ Ρ equivalent source and the metal oxide molar ratio is preferably Ο [0023] Ο [ 0024140716 (ΑΗΜ): ρ=ι .〇η , . 2 b to U. wherein A1, Μ and Ρ are respectively the aluminoin in the aluminum, the metal element of the metal oxide and the phosphorus More preferably, the molar ratio is (α1+μ): ιμ: 2·5^: 3. The mixing in the liquid solvent may be the source, the name The source and the metal oxide are simultaneously or separately added to the liquid phase solvent for mixing; the dish source may be first configured as a solution, and the aluminum crucible and the metal oxide may be added to the phosphonium solution simultaneously or sequentially. In the mixing, wherein the order in which the aluminum source and the metal oxide are added does not affect the final reaction product. In the embodiment of the invention, the η3ρ〇4 aqueous solution is first disposed, and then the human 1 (01〇3 powder is added to the solution). In a 113??4 aqueous solution, after a period of reaction, an Alp〇 white suspension is formed, and then ACr is added to the white suspension. 〇 powder, after 3 hours, the white suspension gradually disappears, and finally the solution becomes a red clear solution. Step 2 above may further comprise a stirring and/or heating step to make the scale source, aluminum source and metal oxide The mixing in the liquid phase solvent is more uniform and the reaction is more complete. The heating temperature is preferably 6 (TC to l〇〇ec Form No. A0101, page 9 / total 40 pages 0992070874-0 201222917, the reaction The time is preferably 2 to 3 hours. [0025] Example 1: Preparation of a lithium ion battery modifier [0026] 34.5 grams of 85% concentration of 113? 〇 4 and 14 grams of deionized water were added to the beaker to configure a solution; magnetic force at 80 ° C The solution was stirred for 5 minutes; 5.9 g of Α1(ΟΗ)3 was added to the above beaker and reacted for 2 hours. The solution in the beaker formed a sol-like liquid; then, 2.5 g of CrOq powder was added to the beaker, and the continuation was continued. The reaction was allowed to proceed for 2 hours to turn the product in the beaker into a clear red solution. [0027] (II) Application of Lithium Ion Battery Modifier [0028] (1) For Lithium Ion Battery Current Collector The above lithium ion battery modifier can be used to improve the stability of a lithium ion battery. Taking the lithium ion battery current collector as an example, since the modifier is a clear solution, it is easy to uniformly coat the surface of the lithium ion battery current collector, and after drying and the like after coating, a uniform and thin surface can be formed on the current collector surface. The protective film prevents the side reaction between the current collector and the lithium ion battery electrolyte and does not affect the conductivity of the current collector. [0030] An embodiment of the present invention further provides a method for using the above lithium ion battery modifier, the method comprising the following steps: [0111] S11, applying the lithium ion battery modifier to a surface of a lithium ion battery current collector A coating layer, and [0032] S12, heat treats the coated lithium ion battery current collector. [0033] In the above step S11, the lithium ion battery current collector material may be a pure metal such as aluminum, copper or nickel or an alloy containing aluminum, copper or nickel. The lithium ion 099140716 Form No. A0101 Page 10 / Total 40 Page 0992070874-0 201222917 Battery modifier can be applied by knife coating, brushing, spraying, electrostatic coating (1) tr〇static coating, adhesive roller (r〇u (3) uniformly applied to one or both surfaces of the collected ion battery collector as in (4) screen printing or pulling. The coating layer should not be too thick, too thick to reduce the conductivity of the current collector. The pulling method can make the coating layer formed on the two sides of the current collector uniform and continuous, and can better control the thickness of the coating layer, so the embodiment of the invention adopts the pulling method in the lithium ion. The two surfaces of the battery current collector are coated with the lithium ion battery modifier. [34] The specific process of the lifting method of the embodiment of the present invention includes: fully infiltrating the lithium ion battery sputum to .. The well-configured plasma ion battery modifier: the bridging the infiltrated lithium ion battery current collector is pulled out of the modifier. When pulling, the clock ion battery current collector can be The modifier page is basically silky straight. The above steps of infiltration and lifting can be repeated several times. Controlling the thickness and uniformity of the current collector surface coating layer. It can be understood that 'the lower the concentration of the above-mentioned cerium ion battery modifier' and the higher the speed at which the infiltrated current collector is pulled out of the modifier Fast, the thinner the thickness of the coating layer formed.

Q

[0035] In the above step S12, before the performing the heat treatment step, the method further includes the step of pre-drying the coated ion battery to evaporate the solvent in the coating layer. The drying method may be dry at room temperature. Dry can also be dried by heating. [0036] The heat treatment step may further evaporate the solvent in the coating layer on the one hand; on the other hand, the evaporated coating layer may be converted into a continuous protective film formed on the surface of the current collector of the ionic battery. The protective film protects the current collector from the corrosion of the electrolyte of the ionic battery. The temperature of the heat treatment 099140716 Form No. A0101

Page 11 of 40 I 0992070874-0 201222917 degrees are from 100 ° C to 350 ° C, preferably, the temperature is from 150 t to 250 t. The heat treatment time is preferably from 1 hour to 3 hours. The protective film may have a thickness of 10 nm to 200 nm, preferably 50 nm to 60 nm. [0040] Referring to FIG. 1, an embodiment of the present invention further prepares a lithium ion battery current collector 100 using the above-mentioned chain ion battery modifier, and the lithium ion is used. The battery current collector 100 includes a metal piece 102 and a protective film 106 disposed on the surface of the metal piece 1〇2. Wherein the composition of the protective film 106 is Α1 Μ PO and X y 4 for a long time

One of AlxMy(P〇3)3 or a mixture of the two; wherein the valence of μ is k ' , or one of Cr, Zn, Cu, Mg, Zr, Mo, V, Nb, and Ta or a mixture of plural; 〇 <x<l,. The material of the metal piece 102 may be a pure metal such as aluminum 'copper or nickel or an alloy containing inscriptions, copper or nickel. The thickness of the metal piece 102 is preferably from 0 to (10) #Π1 ', preferably from 10 mm to 3 mm. The protective film 1〇6 may have a thickness of 10 nm to 200 nm, preferably 50 nm to 60 nm. Preferably, the composition of the protective film is one of AlxCrl x P〇4 and a mixture of the two. The clock ion current collector 100 can be prepared by the following method. S21, providing a lithium ion battery modifier prepared by the above method and a metal sheet 102; S22, applying the lithium ion battery modifier to the surface of the metal sheet The coating layer, and S23, heat-treats the coated metal sheet 1Q2, and the coating layer is converted into a protective film 106 formed on the surface of the metal sheet 102. 099140716 Form No. A0101 Page 12/Total 40 Page 0992070874-0 201222917 [0044] [0045] In the above step S21, the metal piece 102 may be a pure metal such as aluminum, copper or nickel or contain aluminum. An alloy such as copper or nickel. The thickness of the metal piece 102 is preferably 5//111 to 60//111, and the width is preferably 10_ to 30〇111111. In the embodiment of the present invention, an aluminum foil is used as the metal piece 102. The above step S22 can uniformly coat the lithium ion battery modifier by means of blade coating, brush coating, spray coating, electrostatic coating, roll coating, screen printing or pulling. Covering one or both surfaces of the metal sheet 102. The coating layer should not be too thick, too thick to reduce the electrical conductivity of the metal sheet 102. The pulling method can make the coating layer formed on the two surfaces of the metal piece 102 uniform and continuous, and can better control the thickness of the coating layer, so the embodiment of the invention adopts the pulling method to Both surfaces of the metal sheet 102 are coated with the lithium ion battery modifier. The specific process of the pulling process includes: wetting the metal sheet 102 into the prepared lithium ion battery modifier; and pulling the wetted metal sheet 102 out of the modifier. The metal sheet 102 can be made substantially perpendicular to the level of the modifier during pulling. The above steps of wetting and pulling may be repeated a plurality of times to control the thickness and uniformity of the surface coating layer of the metal piece 102. It can be understood that the smaller the concentration of the above lithium ion battery modifier, and the faster the speed of pulling the wetted metal sheet 102 out of the modifier, the more the thickness of the coating layer formed. thin. In the above step S23, before the heat treatment step, the step of drying the coated metal sheet 102 may be further included to remove the solvent in the coating layer, and the drying method may be natural drying at room temperature or heating. dry. 099140716 Form No. A0101 Page 13 / Total 40 Page 0992070874-0 [0046] 201222917 _7] The heat treatment step - the aspect of the liquid phase solvent in the coating layer can be further evaporated; on the other hand, the evaporation can be carried out The subsequent coating layer is converted into a continuous protective film 106 formed on the surface of the metal sheet 102, which protects the metal sheet 102 from corrosion by the lithium ion battery electrolyte. The protective film 106 may have a thickness of from i 〇 nm to 2 〇〇 nm, preferably from 5 至 to 6 〇. The temperature of the heat treatment is 1 〇 (TC to 35 (rc, preferably, the temperature is 150 ° C to 250 ° C. The heat treatment time is preferably 丨 hour to 3 hours. [0048] due to the embodiment of the present invention The lithium ion battery modifier is a clear solution, and a thin and uniformly read protective film 1〇6 can be formed on the surface of the metal piece 102 of the lithium ion battery current collector relatively easily, thereby being better Protecting the lithium ion battery current collector 1 from corrosion, and having little influence on the conductivity of the lithium ion battery current collector 1 [ [ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ And a lithium ion battery current collector having a protective film, and testing the stability of the lithium ion battery current collector having the protective film and the lithium ion battery current collector not coated with the protective film under an acidic environment. [0050] Example 2: Preparation of Lithium Ion Battery Current Collector Inventive Example The above-described chain ion battery modifier was used to prepare a clock ion battery current collector having a protective film. In the embodiment of the present invention, (4) is the metal piece ' The thickness of the metal piece is 2 //m, the width is 3〇mm. The preparation process of the chain ion-packed pool current collector is: adding 0'5ml of Triton and 3〇11]1 water to the prepared lithium ion battery modifier. Ultrasonic shaking for 20 minutes to make it evenly mixed; then applying the modifier to the surface of the box to form a coating layer by pulling; then placing the coating with the coating layer 099140716 Form No. A0101 Page 14 / Total 40 pages 0992070874-0 201222917

[0052] [0055] [0055]

[0057] 099140716 was dried in an oven at 80 ° C for 0.5 hours, and finally the coated aluminum foil was placed in a muffle furnace and incubated at 200 ° C for 1 hour, the invention was obtained. A lithium ion battery current collector having a protective film prepared in the examples. The thickness of the protective film was 52 nm. The concentration of the lithium ion battery modifier is 0.024 g / ml, and the concentration is the total mass of the phosphate in the phosphate source, the aluminum in the trivalent aluminum source, and the metal in the metal oxide. Volume density of volume. Referring to Fig. 2 and Fig. 3, it can be found by scanning electron microscopy that the surface of the conventional aluminum current collector has many defective pits; and the surface of the current collector having the protective film of the present invention is dense and smooth. Test Experiment The lithium ion battery current collector of the embodiment of the present invention and the aluminum current collector not coated with the modifier were respectively placed in a dilute hydrochloric acid solution for observation. The concentration of dilute hydrochloric acid in this test was 1 mol/L. It was observed that the aluminum current collector not coated with the modifier was placed in dilute hydrochloric acid for a period of time to generate bubbles, indicating that the current collector had been corroded; whereas the lithium ion battery current collector of the present invention was soaked in dilute hydrochloric acid. After hours, no bubbles were found on the surface of the current collector, indicating that the current collector was not corroded. In addition, the current collector of the protective film was tested for electrical conductivity, and it was proved that the current collector still has good conductivity and can meet the requirements of the current collector of the lithium ion battery. (2) Electrode for Lithium Ion Battery Referring to FIG. 4, an embodiment of the present invention provides a lithium ion battery electrode 200 including a lithium ion battery current collector 202, an electrode material layer 204, and a form number A0101. Page 0992070874-0 201222917 Lai 6 placed on the layer of electrode material. Wherein, (4) protective film 2〇6: the composition is Α1χΜγΡ〇4 and Α1χ~(p〇3)3 of the species or the two substances; wherein «the valence state is k, M can be Cr, Zn , a mixture of one or more of Cu, Mg, Ζι·, Mo, V, Nb, and Ta; oqu 〇 <y<l and 3x + ky = 3. The protective film 206 is made of the aforementioned lithium ion battery modifier. [0058]

The material of the lithium ion battery current collector 202 may be a pure metal such as aluminum, copper or nickel or an alloy containing aluminum, copper or nickel. The electrode material layer 2〇4 includes an electrode active material, a conductive agent, and a binder. The electrode active material may be a positive electrode active material or a negative electrode active material, and the positive electrode active material may be undoped or doped spinel structure lithium manganate, layered acid clock, lithium nickelate, cobalt acid One or a plurality of lithium, lithium iron phosphate, lithium nickel manganese oxide, and lithium nickel cobalt manganese oxide. Specifically, the tellurite structure of the acid clock can be represented by the chemical formula LixMn2 yLy 〇 4, the acid clock can be represented by the chemical formula LixNii-vLv02, the chemical formula of the sulphur acid can be represented by LixCoi-yLy 〇 2, the layer ▲ acid The chemical formula of the clock can be represented by LixMni-yL, and the chemical formula of the lithium iron phosphate can be represented by Li Fe l PO y L x 1-yy u4, and the chemical formula of the lithium nickel manganese oxide can be

Li 。 Li Li 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学 化学

XCQ 6 Γ Z 1· 1 '〇Sy<l, 〇Sz<1.5,0Sa-z<0.5, 〇Sb + z<1.5 ' 〇<c<l, 〇<d<l, 〇<e< l, 0SfS0.2, c + d + e + f = i. L and R are selected from one or more of a metal element, a soil metal element, a group 13 element, a group 14 element, a transition group element, and a rare earth element. Preferably, L and R are selected from the group consisting of Mn, Ni, and Cr. , Co, V, Ti, Al, Fe, 099140716 Form No. A0101 Page 16 of 40 Page 0992070874-0 201222917

At least one of Ga, Nd, and Mg. The negative electrode material may be one or a plurality of lithium titanate, graphite, organically cracked carbon, and mesocarbon microbeads (MCMB). Specifically, the lithium titanate can be represented by the chemical formula Li A Ti or (4-g) g 5 12 1^/}11^(5 outer) 〇12, wherein 〇<§$〇.33, and 0 <^1 ^0.5; A is selected from one or more of a metal element, a soil metal element, a group 13 element, a group 14 element, a transition group element, and a rare earth element, preferably Mn, Ni, Cr, Co, V, At least one of Al, Fe, Ga, Nd, Nb, and Mg. The conductive agent may be one or more of graphite, acetylene black and carbon nanotubes; the binder may be one or more of PVDF, polytetrafluoroethylene (PTFE) and SBR. It is to be understood that the electrode active material, the conductive agent, and the binder may be other commonly used materials. The composition of the protective film 206 is preferably one of Al Cr P0 and X , -1 - X 4 Α1χ〇1χ(Ρ〇3)3 or a mixture of the two. [0059] The lithium ion battery electrode 200 can be prepared by the following steps: [0060] S31 'forms an electrode material layer 204 on the surface of the inner ion current collector 202; 〇[0061] S32, the lithium ion battery is modified The agent is coated on the surface of the electrode material layer 2〇4 to form a coating layer, and [0062] S33, heat-treating the coated lithium ion battery current collector 2〇2, and the honey coating layer is transformed into the protective film 206. On the surface of the electrode material layer 204. The step S31 may further include: slurrying the electrode active material particles, the conductive agent, and the binder, and applying the (4) to the surface of the silver ion battery current collector 202 to form the electrode material layer 2〇4 ^ In addition, the step of heat-treating the electrode material layer 204 to make it better adhere to the surface of the lithium ion battery current collector 202 described in Form No. A0101, page 17 / page 40, 0992070874-0 201222917. [0067] [0067] In the above steps, since the modifier is a clear solution, the method of uniformly coating the surface of the electrode material layer 2Q4 is easy. Scrape, brush, spray, electrostatic coating, r〇uc〇ating or screen printing. The coating layer should not be too thick, too thick to reduce the conductivity of the (four) subcell electrode. In the above step S33, the heat treatment may evaporate the solvent in the coating layer; on the other hand, the evaporated coating layer may be converted into a continuous protective film 206 formed on the electrode material layer 2 The surface of the electrode material 204 is protected by a surface of 〇4. The temperature of the heat treatment was 1 Torr. (: to 2 〇〇. (: The heat treatment time is preferably from 1 hour to 3 hours. The thickness of the protective film 2〇6 may be from 10 nm to 200 nm, preferably from 5 〇 nm to 60 nm. Since the protective film is thin, Therefore, the conductivity of the lithium ion battery electrode 2 〇 0 is not significant. Referring to FIG. 5 , an embodiment of the present invention further provides a lithium ion battery electrode composite material 300 , which is an electrode composite material 3 g g electrode active material particles And a protective film 3〇6 coated on the surface of the electrode active material, the surface of the protective film 306 is Α1 Μ P0, and one of Α1 Μ (P0)

Xy 4 x y 3 3 1 J or a mixture of the two; wherein, M has a valence of k and M is Cr,

a mixture of one or more of Zn, Cu, Mg, Zr, Mo, V, Nb, and Ta; 0 < χ < 1, 0 < y < l and 3 x + ky = 3. The protective film 306 is coated on the surface of the electrode active material particles 3〇2 by the aforementioned lithium ion battery modifier and is produced by heat treatment. The protective film 306 is uniformly and continuously coated on the surface of the electrode active material particles 099140716, Form No. A0101, page 18/40 pages 0992070874-0 201222917 302, and the mass percentage of the protective film 306 in the electrode composite 300 is preferably 0 to 3%, the thickness is preferably 5 nm to 100 nm. The material of the electrode active material particles 30 2 may be a positive electrode active material or a negative electrode active material. The positive active material may be undoped or doped spinel structure lithium manganate, layered lithium manganate, lithium nickelate, lithium cobaltate, lithium iron phosphate, lithium nickel manganese oxide and lithium nickel cobalt One or more of manganese oxides. Specifically, the spinel structure lithium manganate may be a chemical formula of Li Mn. LyOj indicates that the nickel acid chain can be represented by the chemical formula Li Ni, L 0〇 x 2-y 4 x 1 -y y 2 , and the chemical formula of the acid clock can be Li Co, L 0 . It is indicated that the chemical formula in the layer x 1-yy 2 O-like acid can be obtained by LixMnl yLy〇2, and the chemical formula of the iron phosphate can be represented by Li Fe, L P0, the chemical formula of the lithium nickel manganese oxide X 1 -yy 4 It can be represented by Li Nin Μη, the chemical formula of the 轱 轱 氧 X 0.5+za 1.5-zb ab 4 compound can be represented by Li Ni Cojn, where O.lSx xcdef 2

Sl.l,0Sy<l,0Sz<1.5,0Sa-z<0.5, OS b+z<1.5,0<c<l,0<l<l,0<e<l<l,0SfS0.2, c+d + e + f = l. L and R are selected from the group consisting of a metal element, a soil metal element, a group 13 element, a group 14 element, a transition group element, and a rare earth element. Preferably, L and R are selected from the group consisting of Mn and Ni. , Cr ' Co, V,

At least one of Ti, Al, Fe, Ga, Nd, and Mg. The negative active material may be one or a plurality of lithium titanate, graphite, organic cracked carbon, and mesocarbon microbeads (MCMB). Specifically, the lithium titanate may be represented by the chemical formula LiU_g)AgTi5〇12 or Li4AhTi(5_h)012, wherein '0' 0.33, and 0<hSO. 5 ; A is selected from the group consisting of alkali metal elements, alkaline earth metal elements, and 13th group One or a plurality of the element, the group 14 element, the transition group element, and the rare earth element are preferably at least one of Mn, Ni, Cr, Co, V 'A1, Fe, Ga, Nd, Nb, and Mg. The electrode active material particles 099140716 Form No. A0101 Page 19 of 40 0992070874-0 201222917 The particle size of the particles 302 is preferably from 100 nm to 100 μm. It will be understood that the electrode active material may be made of other commonly used materials. In the embodiment of the present invention, graphite powder having a particle diameter of 8 μm to 12 μm is used as the negative electrode active material particles. The composition of the protective film 306 is one of A1 Cr, PO, and X 1 -X 4 A1 Cr, (POQ) Q or a mixture of the two. X 1 -X 3 3 [0068] The embodiment of the present invention further provides a method for preparing the lithium ion battery electrode composite 300 by using the above lithium ion battery modifier, and specifically includes the following steps: [0069] B11, providing the lithium An ion battery modifier and the above electrode active material particles 30 2; [0070] B12, mixing the electrode active material particles 302 and the lithium ion battery modifier to form a mixture, and [0071] B13, drying and heat treating the mixture . [0072] In the above step B11, the material of the electrode active material particles 302 may be a positive electrode active material or a negative electrode active material. The positive active material may be an undoped or doped spinel structure of lithium manganate, layered lithium manganate, acid-recording chain, acid chain, iron-filled iron, Lie volcanic oxide and Lilu One or more of the manganese oxides. Specifically, the spinel-structured lithium manganate may be represented by the chemical formula Li L 0 , and the lithium nickelate may be represented by a chemical formula X 2-y y 4 , Li Ni, L , and the chemical formula in the succinic acid may be X 1 -y y 2

Li Co, LyC^ indicates that the chemical formula in the layered acid can be X 1 -y 2

Li Mni-yL, the chemical formula of the iron in the wall can be represented by Li Fe, L PO, x y 2 x 1-y y 4 , and the chemical formula of the manganese oxide can be

Li N i. , Μηι. 5-z-bL indicates that the nickel-nickel manganese oxide X 0.5+za ab 4 099140716 Form No. A0101 Page 20 of 40 0992070874-0 201222917 The chemical formula can be represented by LixNicC〇dMneLf02. Where 〇. 1,1 ' 0$y&lt;l ' 0$z&lt;1.5,〇Sa-z&lt;0.5,0gb + z&lt;1.5 ' 0&lt;c&lt;1 ' 〇&lt;d&lt;l,〇&lt;e&lt; l, 0SfS0.2, c + d + e + f = l. L and R are selected from one or more of a metal element, a soil metal element, a group 13 element, a 14th private element, a transition element, and a rare earth element. Preferably, L and R are selected from the group consisting of Mn, Ni, and Cr. At least one of Co, V, Ti, Al, Fe, Ga, Nd, and Mg. The anode active material may be one of lithium titanate, graphite, organic cracked carbon, and mesocarbon microbeads (MCMB) or Multiple species. Specifically, the lithium titanate may be represented by the chemical formula L1(4-g)AgTi5(h2 or Li4AhTi(5h)〇12, wherein 0.33' and 0 &lt;h$〇5; a is selected from the group consisting of alkali metal elements, soil metal elements, One or more of the Group 13 element, the Group 14 element, the transition group element, and the rare earth element, preferably at least one of Mn, Ni, Cr, C〇, V 'Al, Fe Ga, Nd, Nb, and Mg The particle size of the electrode active material particles 302 is preferably from 100 nm to 100 μm. It is understood that the material of the electrode active material particles 302 can also be used in other commonly used materials. In the embodiment of the present invention, the particle size is 8 μm. The graphite powder to 12 μm is used as the negative electrode active material particles. [0073] In the above step B12, the mixing is solid-liquid mixing, and the electrode active material particles 302 are insoluble in the lithium ion battery modifier. The ion battery modifier is a clear solution and has a certain viscosity. Therefore, the β-coating agent is easy to uniformly adhere to the surface of the electrode active material particles 3 〇 2 to form a thin layer of the modifier layer. [0074] In addition, the electrode active material When the particle 3〇2 is mixed with the modifier, it is only necessary to enable the modifier to cover the surface of the electrode active material particle 3 〇 2 to be 099140716 Form No. 1010101 Page 21 / Total 40 Page 0992070874-0 201222917 The mixture is in the form of a slurry, which is advantageous for obtaining the surface-coated thin electrode active material particles 3 0 2 . [0075] After the above step B12, a filtering step may be further included to filter out the excess ionic battery in the mixture. In the above step B13, the drying treatment may be natural drying or heating and drying at normal temperature to remove the solvent in the mixture, and the temperature of the heating and drying is preferably 60° C. to 100°. C. In the embodiment of the present invention, the mixture is dried at 80 ° C. The heat treatment can convert the modifier layer on the surface of the electrode active material particles 302 to a uniform continuous protective film 306 after the drying. The surface of the electrode active material particle 302 is coated to obtain the lithium ion battery electrode composite material 300 according to the embodiment of the present invention. The temperature of the heat treatment is preferably 30 (TC~800 ° C, and the heat treatment time is preferably 1 hour to 3 hours). 5%至至3%, the mass percentage of the protective film 306 in the electrode composite material 300 is preferably 0.5% 〇 to 3%, in the embodiment of the present invention, the heat treatment is performed at a temperature of 700 ° C, the heat treatment time is 3 hours. The thickness is preferably from 5 nm to 100 nm. [0077] Since the lithium ion battery modifier in the embodiment of the present invention is a clear and viscous solution, a protective film can be formed on the surface of all the electrode active material particles relatively easily. The surface of each electrode active material particle is completely covered by the protective film, and the protective film coated on the surface of the electrode active material particle is thin and uniform, and the protective film can isolate the lithium ion battery electrolyte and the electrode. The electron migration between the active material particles causes the ions to pass, thereby avoiding the side reaction between the lithium ion battery electrode and the electrolyte on the one hand, improving the thermal stability of the battery and the battery capacity retention performance, and on the other hand The electrode active material particle surface 099140716 Form No. A0101 Page 22 / Total 40 page 0992070874-0 201222917 The protective film is thin and does not reduce lithium ion electricity The electrochemical properties. [0078] (3) For Lithium Ion Battery Separator [0079] Embodiments of the present invention also provide a method for preparing a plasma cell separator using the lithium ion battery modifier, comprising the following steps: [0080] B21 'provided a porous film for a lithium ion battery separator and the above lithium ion battery modifier; [0〇81] B22, the modifier is applied to the surface of the porous film to form a coating layer, and 〇C0082] B23, dried and coated The porous film coated with the modifier forms a modifier layer on the surface of the porous film. In the above step B21, the porous film may be a known separator for a lithium ion battery, such as a pure polymer separator, a ceramic separator or a polymer separator containing a ceramic material. The porous film may have a thickness of 5 μm to 6 μm, and preferably, the porous film has a thickness of 5 μm to 4 μm. The porous film may have a porosity of 20% to 90% and a pore diameter of 〇1 μm to 8 μm. Preferably, the porosity is 40% to 80% and the pore diameter is 〇 1 μm. The present invention employs a poly(tetra)(PP) microporous membrane as the porous membrane, and the far microporous membrane has a porosity of 6 〇%' average pore diameter of 7 μm. The porous film can be prepared by a conventional method such as a smear stretching method or a thermally induced phase separation method. [0084] In the above steps, it can be difficult, sprayed, electrostatically coated, bonded, screen printed or The singularity of the porous film is applied to one or both surfaces. Since the coating: coating for the solution, the pulling method can make the coating film formed by the surface porous film (four) 099140716 Form No. A0101 Page 23 / Total 4 page 0992070874-0 201222917 uniform and continuous, and better The thickness of the coating layer is controlled, so that the lithium ion battery modifier is coated on both surfaces of the porous film by a pulling method in the embodiment of the present invention. [0085] The specific process of the pulling method comprises: completely infiltrating the porous membrane into the prepared lithium ion battery modifier; and pulling the infiltrated porous membrane out of the modifier . At the time of pulling, the porous membrane can be made substantially perpendicular to the level of the modifier. The above steps of wetting and pulling may be repeated plural times to control the thickness of the coating layer on the surface of the porous film and the uniformity. It can be understood that the smaller the concentration of the above-mentioned lithium ion battery modifier, and the faster the speed at which the infiltrated porous film is pulled out of the modifier, the thinner the thickness of the coating layer formed. 〇lmol/L。 The concentration of the modifier in the embodiment of the present invention is 0. 〇lmol / L. [0086] In the above step B23, the drying step may remove the solvent in the lithium ion battery modifier and better form the modifier layer to be bonded to the surface of the porous film. The drying method may be naturally dried at room temperature or dried by heating, and the drying temperature is not higher than 70 °C. The modifier layer may have a thickness of 10 nm to 100 nm, and preferably, the modifier layer has a thickness of 10 nm to 40 nm. In the embodiment of the present invention, the coated porous film was dried at 40 ° C to better bond the formed modifier layer to the surface of the porous film. [0087] Since the lithium ion battery modifier is a clear solution and the thickness of the modifier layer formed is relatively thin, the modifier layer has little effect on the porosity and pore diameter of the porous membrane, When the porous film having the modifier layer is applied to a lithium ion battery, the lithium ion mobility in the lithium ion battery is not affected. 099140716 Form No. A0101 Page 24 of 40 0992070874-0 201222917 [0088] Referring to FIG. 6, a lithium ion battery separator 400 is further prepared by the above method, and the diaphragm 400 includes a porous membrane 402 and A modifier layer 404 disposed on the surface of the porous film 402. The modifier layer 404 is formed by applying the above-described lithium ion battery modifier to the surface of the porous film 402 to form a coating layer, and drying the coating layer. [0089] The porous film 402 may be a conventional separator for a lithium ion battery, such as a pure polymer separator, a ceramic separator, or a polymer separator containing a ceramic material. The porous film 402 may have a thickness of 5 μm to 60 μm. Preferably, the porous film has a thickness of 15 μm to 40 μm. 01微米至80微米。 The porous film may have a porosity of from 20% to 90%, a pore size of from 0.01 microns to 80 microns. Preferably, the porosity is 40% to 80%, and the pore diameter is 0.1 μm to 10 μm. In the present invention, a polypropylene (ΡΡ) microporous membrane having a porosity of 60% and an average pore diameter of 7 μm was used. The porous film 402 can be produced by a conventional melt stretching method or a thermally induced phase separation method. The modifier layer 404 is disposed on both surfaces of the porous film 402. The thickness of the modifier layer 404 may be 1〇11111~10〇11111. Preferably, the thickness of the modifier layer is 10 nm. ~40nm. Since the lithium ion battery modifier is a clear solution and has a certain viscosity, the modifier is easily applied uniformly on the surface of the porous film 402 to form a thinner modifier layer 40. 4. Since the thickness of the modifier layer 404 is thin, the mechanical strength of the separator 400 can be increased without making the coated separator 400 brittle. During use of the lithium ion battery, when the separator 400 is heated to a higher temperature (greater than 100 ° C), the modifier layer 404 is converted into a continuous protective film to better prevent heat shrinkage of the separator 400. The thermal stability of the diaphragm 400 is improved. The protective film 099140716 Form No. A0101 Page 25 of 40 0992070874-0 201222917 The composition of AlxMyP〇4 and AlxMy(P〇3)3 or a mixture of the two substances; wherein the valence of Μ is k , Μ is Cr, Zn, Cu, Mg,

a mixture of one or more of Zr, Mo, V, Nb, and Ta; 〇 &lt;x&lt;i, 〇&lt;y&lt;l and 3x + ky = 3. Preferably, the composition of the protective film is one of A1xCri-xP04 and Al'rv/POPs or a mixture of the two. [0094] In the embodiment of the present invention, the separator of the ion battery (the porous film is polypropylene) is prepared by the above method, and the separator and the polypropylene separator not coated with the modifier are respectively The heat shrinkage rate was measured by holding at different temperatures for 1 hour. Since the separator of the embodiment of the present invention and the polypropylene separator not coated with the modifier have almost no shrinkage in the transverse direction, the longitudinal heat shrinkage ratio of the two separators was mainly tested in the present invention. Referring to FIG. 7, it can be seen from the figure that the lithium ion battery separator of the embodiment of the present invention has better heat shrinkage resistance at different temperatures than the polypropylene buffer without the modifier. Sex. In addition, in the embodiment of the present invention, the above two kinds of separators are respectively assembled into a lithium iron phosphate battery to test the electrochemical performance thereof, and the safety performance is found. It is found that the application of the modifier on the surface of the separator is not reduced in the lithium ion battery. The electrochemical performance of the lithium ion battery, and the lithium ion battery has better thermal stability and improves the safety of the ion battery. (4) For a lithium ion battery, please refer to FIG. 8. The embodiment of the present invention further provides a lithium ion battery, which includes a positive electrode sheet 5, a negative electrode sheet 5〇4, and a separator 5〇6. Non-aqueous electrolyte and external package structure 5〇8. The external package structure 099140716 Form No. A0101 Page 26/Total 4 page 0992070874-0 201222917 508 [0095] 508 The positive electrode sheet 502, the negative electrode sheet 5〇4, the separator 5〇β, and the non-aqueous electrolyte solution are encapsulated therein, The separator 506 is disposed between the positive electrode tab 5〇2 and the negative electrode tab 504. The positive electrode sheet 5〇2 includes a positive current collector 5^2 and a positive electrode material layer 522 formed on the surface of the positive electrode current collector 512. The negative electrode plate 504 includes a negative current collector 514 and a surface formed on the negative current collector. A negative electrode material layer 524. Wherein, at least one of the positive electrode current collector 512, the positive electrode material layer 522, the negative electrode current collector 514, the negative electrode material layer 524, and the separator 506 of the lithium ion battery 5 包括 includes the composition of the lithium ion battery modifier or the modification The agent is a component of the product after being heated by a reaction of rc or more. The modifier is a combination of the phosphorus source containing the root, the trivalent cerium, and the metal oxide in the liquid solvent. The agent is a species of ΑΐχΆ and a, m(10)) or a mixture of the two substances after iq "C or more heat reaction"; wherein the price of ruthenium ^, ^ is ^,

Zn, Cu, Mg, Zr, Mo, V mixed; 0 &lt; χ &lt; 1, 0 &lt; y &lt; 1 and 3 Ο [0096] The composition is a mixture of A1 Cr X species.

1 -X P04U^AlxCr1 : One or a plurality of N + ky = 3 in Nb and Ta. Preferably, one or both of -x(P〇3)3 of the product [0097] the positive electrode sheet 502 and/or the negative electrode sheet 504 may have a corresponding positive electrode material layer and/or negative electrode material in the above embodiment. Layer of the clock ion battery electrode. The cathode current collector 512 and/or the anode current collector ... may be the lithium ion battery current collector 1QG or the hetero battery current collector 2 〇 2 described in the above embodiment. The positive electrode material layer 522 includes a uniformly mixed positive electrode active material, a conductive agent, and a binder. The negative electrode material layer 524 includes a uniformly mixed 099140716 negative electrode active material, a conductive agent, and a binder. The positive electrode active material of the positive electrode material layer 522 including 0992070874-0 201222917 may include the electrode composite material 300 having the positive electrode active material particles described in the above embodiments, and the negative electrode material is similarly formed. The anode active material contained in the layer 524 may include the electrode composite material 300 having the anode active material particles described in the above embodiments. The conductive agent may be acetylene black or carbon fiber or the like, and the binder may be polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE). It is to be understood that the positive electrode active material, the negative electrode active material, the conductive agent and the binder may be other commonly used materials. The separator 506 may be a conventional lithium ion battery separator, such as a pure polymer separator, a ceramic separator or a polymer membrane containing a ceramic material, or the like, or may be the lithium ion battery separator 400 described in the above embodiment. [0099] The electrolyte salt in the electrolyte may be lithium hexafluorophosphate, lithium tetrafluoroborate or lithium bis(oxalate)borate, and the organic solvent in the electrolyte may be ethylene carbonate, diethyl carbonate or dinonyl carbonate. . The outer package structure 508 can be a rigid battery case or a soft package bag. In addition, the lithium ion battery 50 also includes an element (not shown) that electrically connects the internal and external circuits of the battery. Applying the above lithium ion battery modifier to the lithium ion battery can improve the safety performance of the lithium ion battery. [0101] It can be understood that the modifier can be used not only for protecting the current collector, the electrode active material, and the separator, but the application of the modifier in the lithium ion battery or the heat treatment of the modifier to form a protective film is in the present invention. Within the scope of protection. [0102] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only the preferred embodiment of the present invention. 099140716 Form No. A0101 Page 28 of 40 0992070874-0 201222917, it is not possible to limit the scope of patent application in this case. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS [0103] FIG. 1 is a side view of a current collector structure of a lithium ion battery according to an embodiment of the present invention. 2 is a SEM photograph of a conventional lithium ion battery current collector. 3 is a SEM photograph of a current collector of a lithium ion battery according to an embodiment of the present invention. 4 is a side view showing the structure of an electrode of a lithium ion battery according to an embodiment of the present invention. 5 is a schematic structural view of a lithium ion battery electrode composite material according to an embodiment of the present invention. 6 is a schematic side view of a lithium ion battery separator according to an embodiment of the present invention. 7 is a heat shrinkage test chart of a lithium ion battery separator and a conventional separator according to an embodiment of the present invention. 8 is a partial cross-sectional view showing the structure of a lithium ion battery according to an embodiment of the present invention. [Description of main component symbols] [0111] Lithium-ion battery current collector: 100, 202 [0112] Metal piece: 102 [0113] Protective film: 106, 206, 306 099140716 Form No. A0101 Page 29/Total 40 Page 0992070874-0 201222917 [0114] Lithium ion battery electrode: 200 [0115] Electrode material layer: 204 [0116] Electrode composite material: 300 [0117] Electrode active material particles: 302 [0118] Separator: 400,: 506 [0119] Porous film: 402 [0120] Modifier layer: 4 0 4 [0121] Lithium ion battery: 500 [0122] Positive electrode sheet: 502 [0123] Negative electrode sheet: 504 [0124] External package structure: 508 [0125] Positive current collector: 512 Positive Electrode Material Layer: 522 [0127] Anode Current Collector: 514 [0128] Anode Material Layer: 524 099140716 Form No. A0101 Page 30 of 40 0992070874-0

Claims (1)

201222917 VII. Patent application scope: 'The method of using 1 lithium ion battery modifier' includes the following steps: Providing a porous membrane for a separator of a ionic battery and a modifier of a plasma battery, the modifier comprising a phosphate a phosphorus source 'trivalent aluminum source and a mixture of metal oxides in a liquid phase solvent; • applying the modifier to the surface of the porous film to form a coating layer, and drying the porous layer coated with the modifier A film to form a modifier layer on the surface of the porous film. 2. The method of claim 1, wherein the phosphorus source is phosphoric acid, triammonium phosphate, aluminum phosphate, ammonium dihydrogen phosphate, aluminum dihydrogen phosphate, One or more of ammonium monohydrogen phosphate and aluminum monohydrogen phosphate. 3. The method of using a lithium ion battery modifier according to claim 1, wherein the aluminum source is aluminum hydroxide, aluminum oxide, aluminum phosphate, aluminum dihydrogen phosphate, and aluminum hydrogen phosphate. One or more species. 4. The method of claim 1, wherein the source of the phosphorus source is aluminum phosphate, aluminum dihydrogen phosphate, and aluminum hydrogen phosphate. One or more species. 5. The method of using a lithium ion battery modifier according to claim 1, wherein the metal oxide comprises trioxide, oxidized, copper oxide, magnesium oxide, zirconium dioxide, molybdenum trioxide. One or more of oxygen hole-sharp, tantalum pentoxide, and tantalum pentoxide. 6. The method of using a lithium ion battery modifier according to claim 1, wherein the liquid phase solvent is water or fluorenylmethylpyrrolidine. 7. The method of using a lithium ion battery modifier according to the first aspect of the patent application, which is in the form of a lithium ion battery modifier, 099140716, a form number Α0101, a 31st page, a total of 40 pages 0992070874-0 201222917, wherein the phosphorus source, the aluminum source, and The molar ratio of the metal oxide satisfies: (A1 + M): P = 1 : 2 · 5 to 1: 4 ' wherein A1, M and p are respectively aluminum elements in the aluminum source, the metal oxide The metal element in the metal and the number of moles of the phosphorus element in the phosphorus source. The method for using a lithium ion battery modifier according to claim 1, wherein the phosphate of the phosphorus source, the aluminum element of the trivalent aluminum source, and the total mass of the metal element of the metal oxide account for 02克/毫升。 The total volume of the modifier is 0. 02g / ml to 0. 08g / ml. The method of using an ion battery modifier as described in claim 1 wherein the modifier is coated on both surfaces of the porous film. 10 . 11 . 12 . 13 . 14 . 15 . 099140716 The method of using the ionization battery modifier according to claim 1, wherein the drying method is heat drying. A method of using a chain ion battery modifier according to claim 10, wherein the drying temperature is not higher than 7 °C. The invention relates to a plasma membrane separator comprising a porous membrane, the improvement comprising further comprising a layer of a political agent disposed on the surface of the porous membrane, the modifier layer being formed by using a phosphate source containing phosphoric acid and a source of trivalent aluminum The ruthenium metal halide is mixed in a liquid solvent and applied to the surface of the porous film to form a coating layer, which is formed after drying the coating layer. The bell-ion battery separator according to claim 12, wherein the modifier layer is provided on both surfaces of the porous membrane. The bell-ion battery separator according to claim 12, wherein the modifier layer has a thickness of 1 〇 nanometer to 1 〇 〇 nanometer. A lithium ion battery, comprising a positive electrode sheet, a negative electrode sheet, a separator, a non-aqueous electrolyte, and an external package structure, wherein the separator is the clock ion battery according to any one of the above-mentioned claims 12-14. Diaphragm. 0992070874-0 Form No. A0101 Page 32 of 40