CN109713225A - Lithium ion secondary battery - Google Patents

Lithium ion secondary battery Download PDF

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Publication number
CN109713225A
CN109713225A CN201711012117.1A CN201711012117A CN109713225A CN 109713225 A CN109713225 A CN 109713225A CN 201711012117 A CN201711012117 A CN 201711012117A CN 109713225 A CN109713225 A CN 109713225A
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China
Prior art keywords
electrode active
active material
negative electrode
lithium ion
ion secondary
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Inventor
马建军
沈睿
何立兵
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN202111095586.0A priority Critical patent/CN113889620A/en
Priority to CN201711012117.1A priority patent/CN109713225A/en
Publication of CN109713225A publication Critical patent/CN109713225A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a lithium ion secondary battery. The lithium ion secondary battery comprises a positive pole piece, a negative pole piece, an isolating membrane and electrolyte; the positive pole piece comprises a positive current collector and a positive active material coating, wherein the positive active material coating contains Li with a general formulaxNiaCobMcO2Wherein M is at least one selected from Mn and Al, x is 0.95-1.2, a is more than 0 and less than 1, b is more than 0 and less than 1, c is more than 0 and less than 1, and a + b + c is 1; the negative pole piece comprises a negative pole current collector and a negative pole active material coating, the negative pole active material coating comprises a graphitized carbon material with the graphitization degree of 92% -97% as a negative pole active material, and the compaction density of the negative pole active material coating is 1.5-1.8g/cm3. The lithium ion secondary battery has good electrical property and dynamic property.

Description

A kind of lithium ion secondary battery
Technical field
The invention belongs to battery technology field, it is more particularly related to a kind of lithium with high-energy density from Sub- secondary cell.
Background technique
With becoming increasingly popular for electric car, the requirement to battery is also increasingly stringenter.It is required that battery should possess Gao Rong Measure good cyclical stability again.For this purpose, technology people is from anode and negative electrode active material, additive, electrolyte Etc. various aspects be made that a variety of effort.
For battery anode active material, compared to LiFePO4, NCM ternary material have higher gram volume and Compacted density.Therefore, there is higher energy density using the battery core of ternary material.For negative electrode material, graphite material It is preferable with positive electrode matching with good charging/discharging voltage platform, the advantages that battery average output voltage of composition is high, It is a kind of electrode material haveing excellent performance.Its specific volume can effectively be improved by promoting the graphite material lattice degree of order (degree of graphitization) Amount.However, high capacity graphite quality is softer, it is easy to happen deformation after being pressurized in pole piece process, will affect the leaching of electrolyte Profit, and then influence the cycle performance and high rate performance of battery.
In view of this, there is high capacity and good electricity simultaneously it is necessory to provide a kind of lithium ion secondary battery Performance.
Summary of the invention
It is an object of the present invention to: a kind of lithium ion secondary battery is provided, there is high capacity and good simultaneously Chemical property.
Inventor is through many experiments, it was thus unexpectedly found that certain types of battery anode active material and negative electrode active material Material is combined, and can improve the cycle life of lithium ion secondary battery while improving battery core energy density.
Specifically, the present invention provides a kind of lithium ion secondary battery, including anode pole piece, cathode pole piece, isolation film And electrolyte；
Wherein the anode pole piece includes plus plate current-collecting body and positive active material coating, the positive active material coating It is Li comprising general formulaxNiaCobMcO2Positive electrode active materials, wherein M is selected from least one of Mn, Al, 0.95≤x≤1.2,0 1,0 < b < of < a <, 1,0 < c < 1 and a+b+c=1；
The cathode pole piece includes negative current collector and negative electrode active material coating, and the negative electrode active material coating includes Degree of graphitization is the graphitized carbon material of 92%-97% as negative electrode active material, and negative electrode active material coating compacted density is 1.50-1.80g/cm3。
Compared with prior art, by using specific anode and cathode active materials, lithium ion secondary electricity provided by the invention Pond, the advantages of high capacity and long circulation life can be had both.
The invention further relates to the preparation methods of above-mentioned lithium ion secondary battery, comprising:
It 1) the use of general formula is LixNiaCobMcO2Positive electrode active materials prepare positive plate, wherein M is in Mn, Al At least one, 0.95≤x≤1.2,0 < a <, 1,0 < b <, 1,0 < c < 1 and a+b+c=1；
2) it uses the graphitized carbon material that graphitiferous degree is 92%-97% as negative electrode active material, it is living to prepare cathode Property matter coatings compacted density be 1.50-1.80g/cm3Negative electrode tab；
3) negative electrode tab described in positive plate prepared by step 1) and step 2) is assembled into battery.
Specific embodiment
The present invention provides a kind of lithium ion secondary batteries, including anode pole piece, cathode pole piece, isolation film and electrolyte；
Wherein the anode pole piece includes plus plate current-collecting body and positive active material coating, the positive active material coating It is Li comprising general formulaxNiaCobMcO2Positive electrode active materials, wherein M is selected from least one of Mn, Al, 0.95≤x≤1.2,0 1,0 < b < of < a <, 1,0 < c < 1 and a+b+c=1；
The cathode pole piece includes negative current collector and negative electrode active material coating, and the negative electrode active material coating includes Degree of graphitization is the graphitized carbon material of 92%-97% as negative electrode active material, the compacting of the negative electrode active material coating Density is 1.50-1.80g/cm3；
Inventor is it is believed that degree of graphitization is the carbon material of 92%-97% and the compacted density of negative electrode active material coating Control is in 1.50-1.80g/cm3More gap structure can be formed inside pole piece, while guaranteeing battery core energy density The cycle performance of battery core can be promoted.Inventors have found that when degree of graphitization is lower than 92%, negative electrode active material coating on pole piece Compacted density reach 1.70g/cm3, then need to improve cold pressing roller pressure, cause graphite particle structure to be destroyed, be circulated throughout Material side reaction increases in journey, and cycle life is affected.In addition, pole piece rebound is larger when degree of graphitization is lower, lead to reality It is lower using densification, influence the energy density of battery core.When degree of graphitization is higher than 97%, negative electrode active material coating on pole piece Compacted density reaches 1.70g/cm3, since high graphitization degree graphite quality is softer, it is easy to happen deformation after compression, leads to pole piece In intergranular hole reduce, will affect the infiltration of electrolyte, battery core local polarisation increases, and then influences the cycle performance of battery And high rate performance.But it is explained above merely for convenience those skilled in the art understand that the principle of the present invention and provide, It is not construed as limiting the invention；The present invention is also not excluded for that other may be made not to the principle of the present invention with development in science and technology Same theoretical explanation.
Inventor will lead to graphite material it has furthermore been found that when the degree of graphitization of graphite cathode material is greater than 97% Interlamellar spacing becomes smaller.During charge and discharge, volume change caused by the insertion of lithium ion, abjection is larger, will affect SEI layers of (electricity When the initial charge of pond, since electrolyte and negative electrode material react in level between solid liquid phase, formed in negative terminal surface blunt Change layer, i.e. solid electrolyte interface film) stability, so as to cause cycle performance deterioration；And work as the graphite of graphite cathode material When change degree is less than 92%, the crystallinity of graphite is lower, and lattice defect is more, and side reaction easily occurs in cyclic process and causes to hold Amount decaying.By many experiments, it is found that the suitable degree of graphitization of negative electrode material is 92%-97%, preferably 93%-95%.
Inventor is it has furthermore been found that the compacted density when negative electrode active material coating on pole piece is less than 1.50g/cm3When, stone The intergranular contact of ink is poor, influences the consistency of pole piece current density, and battery core polarization is caused to increase.In addition, too small cathode The compacted density of coating layer of active substance will affect battery core energy density, cause battery core energy density relatively low.When cathode is living on pole piece Property matter coatings compacted density be greater than 1.80g/cm3When, intergranular hole is reduced in pole piece, and grain structure is squeezed brokenly It is bad.Electrolyte infiltration is difficult, and polarization increases, and the long-term cycle performance of battery core deteriorates.Therefore, negative electrode active material applies on cathode pole piece The compacted density of layer is 1.50-1.80g/cm3, preferably 1.60-1.70g/cm3。
In order to further increase dynamic performance (the especially high rate performance of battery), the graphite cathode material surface is also There can be clad.Clad is usually amorphous carbon, such as selected from least one of carbon black, coke, soft carbon, hard carbon.It should Amorphous carbon is usually 2-13% relative to the content of the electrode material total weight, preferably 2-10%.In some embodiments In, the amorphous carbon be by selected from selected from coal tar pitch and petroleum asphalt, mesophase pitch, epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, polyethylene oxide, Kynoar, acrylic resin and polypropylene At least one of nitrile material is through obtained from (high temperature) charing.
Lithium ion secondary battery of the invention can use the above specific positive electrode and negative electrode material using this field It is prepared by well known method.Lower mask body introduction.
1, prepared by positive plate:
In general, positive electrode active materials, conductive agent, binder etc. are mixed by certain weight ratio, solvent is added, true It is stirred evenly under empty blender effect, obtains anode sizing agent；Anode sizing agent is evenly applied to plus plate current-collecting body (such as aluminium foil) On；The plus plate current-collecting body for being coated with anode sizing agent is transferred to oven drying, then obtains anode pole piece by cold pressing, cutting.
Positive electrode active materials used in the present invention are LixNiaCobMcO2, wherein M is selected from least one of Mn, Al, 1,0 < b < of 0.95≤x≤1.2,0 < a <, 1,0 < c < 1 and a+b+c=1.This is lithium battery tertiary cathode commonly used in the art Material.When M is Mn, abbreviation NCM ternary material；When M is Al, abbreviation NCA ternary material.NCM ternary material and NCA ternary material It is all known that there is energy density more higher than LiFePO4, and be battery material commonly used in the art, it can be logical from many suppliers Cross commercial sources acquisition.
Specifically, the positive electrode active materials can be selected from LiNi0.33Co0.33Mn0.33O2、LiNi0.5Co0.2Mn0.3O2、 LiNi0.5Co0.25Mn0.25O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.85Co0.1Mn0.05O2、 LiNi0.8Co0.15Al0.05O2At least one of.
In a preferred embodiment of the invention, the weight of the positive electrode active materials accounts for positive active material coating 92%-98%.
In certain embodiments of the present invention, the positive electrode active materials can also by selected from Al, Zr, Ti, B, Mg, V, At least one of Cr, F element doping, to be further improved battery performance.
In certain embodiments of the present invention, the surface topography of the positive electrode active materials can be into one at clad Step improves battery performance, and the clad compound can for example contain at least one of Al, Zr, Ti, B element.
2, prepared by negative electrode tab:
1) preparation of negative electrode material
In the present invention, " graphitized carbon material " has the normally understood meaning of those skilled in the art institute, that is, is suitable for Inside for cell negative electrode material is mainly in the carbon material of graphite laminated structure.Graphitized carbon material can be natural graphite, people Make the mixture of graphite, or both.Can for example it lead to for the graphitized carbon material that graphitiferous degree of the present invention is 92%-97% Following method is crossed to be prepared:
(1) needle coke after needle coke after petroleum forging or coal measures forging is crushed, obtaining average grain diameter is 5-20 μm Raw material；
(2) Shape correction is carried out to raw material in (1), it is (excellent so as to adjust raw material particle size distribution then carries out classification processing again Selection of land, removes bulky grain of the partial size greater than Dv90 and partial size is less than the little particle of Dv10)；
(3) high temperature graphitization processing is carried out to the raw material after shaping screening in (2), for example, in acheson furnace It is carried out at a temperature of such as 2800-3250 DEG C (preferably 2850-3200 DEG C)；
(4) material obtained in (3) is sieved, except obtaining required negative electrode material after magnetic.
Shape correction in step (2) is the common processing method in artificial graphite preparation process, is those skilled in the art Known to member, any reshaping machine or other shaping devices commonly used in the art can be used and carry out.Classification processing in step (2) Classifying screen commonly used in the art (sieve method), gravity selector, centrifugal separator etc. can be used to realize.Optionally, in step Suddenly cladding carbonization can be carried out after (3), before step (4), i.e., by the product of (3) acquisition and selected from coal tar pitch, petroleum Pitch, mesophase pitch, epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polyvinyl chloride, poly- second two The mixing of at least one of alcohol, polyethylene oxide, Kynoar, acrylic resin and polyacrylonitrile material, carries out pyrocarbon Change processing.The temperature of charing process is for example at 900-1500 DEG C, such as 1000-1400 DEG C or 1100-1300 DEG C.
Alternatively, the present invention can also directly using meet degree of graphitization be 92%-97% natural graphite or commercially available graphite Change carbon material.
The size of the degree of graphitization of the graphitized carbon material can be measured with method known in this field, such as with X-ray diffractometer be measured (such as may refer to Qian Chongliang etc., " degree of graphitization of XRD determining carbon material ", " Central-South work Industry college journal " the 3rd phase of volume 32, in June, 2001).
2) assembling of negative electrode tab
Negative electrode active material, thickener, binder etc. are mixed by constant weight, addition solvent (such as deionization Water), stable negative electrode slurry is obtained under de-airing mixer effect；Negative electrode slurry is uniformly coated in negative current collector (example Such as copper foil) on；The negative current collector for being coated with negative electrode slurry is transferred to oven drying, is then born by cold pressing, cutting Pole pole piece.
In the above preparation method, can by adjust cold pressing process in cold pressing device rolling pressure or roll gap gap come Control the compacted density of resulting negative electrode active material coating when pole piece rolling.
In a preferred embodiment of the invention, the weight of the negative electrode active material accounts for negative electrode active material coating 92%-98%.
3, electrolyte quota:
As nonaqueous electrolytic solution, usually using the lithium salt solution dissolved in organic solvent.Lithium salts is, for example, LiClO4、 LiPF6、LiBF4、LiAsF6、LiSbF6Equal inorganic lithium salts or LiCF3SO3、LiCF3CO2、Li2C2F4(SO3)2、LiN (CF3SO2)2、LiC(CF3SO2)3、LiCnF2n+1SO3Organic lithium salts such as (n >=2).Organic solvent example used in nonaqueous electrolytic solution The cyclic carbonates such as ethylene carbonate, propene carbonate, butylene, vinylene carbonate in this way, dimethyl carbonate, carbonic acid The linear carbonates such as diethylester, methyl ethyl carbonate, the chains ester such as methyl propionate, the cyclic esters such as gamma-butyrolacton, dimethoxy second The chains ether such as alkane, diethyl ether, diethylene glycol dimethyl ether, triglyme, the cyclic ethers such as tetrahydrofuran, 2- methyltetrahydrofuran, The mixture of the nitriles such as acetonitrile, propionitrile or these solvents.
For example, by ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) according to certain volume ratio into Row mixing, then by sufficiently dry lithium salts LiPF6It is dissolved in mixed organic solvents, is configured to electrolyte.
4, isolation film:
For isolation film without particular/special requirement, can be selected according to actual needs, specifically, the optional autohemagglutination of isolation film Vinyl film, polypropylene screen, polyvinylidene fluoride film and their multilayer complex films.
5, prepared by full battery:
Above-mentioned anode pole piece, isolation film, cathode pole piece are folded in order, isolation film is between positive and negative plate and rises To the effect of isolation, then winding obtains naked battery core；Naked battery core is placed in outer packing shell, the above-mentioned electrolyte prepared is infused Enter in the naked battery core to after drying, by processes such as Vacuum Package, standing, chemical conversion, shapings, obtains lithium ion battery.
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, with reference to embodiments The present invention is described in further detail.However, it should be understood that the embodiment of the present invention is of the invention just for the sake of explaining, and It is non-in order to limit the present invention, and the embodiment of the present invention is not limited to the embodiment provided in specification.It is not infused in embodiment The routinely condition of bright experiment condition makes, or makes by the condition that material supplier is recommended.
Embodiment
Embodiment 1
The battery of embodiment 1 is prepared as follows.
1, prepared by anode pole piece: by LiNi0.6Co0.2Mn0.2O2, SuperP (conductive agent), PVDF (binder) in mass ratio 97:1:2 is mixed, and solvent is added, and is stirred evenly under de-airing mixer effect, is obtained anode sizing agent；Anode sizing agent is equal It is even to be coated on plus plate current-collecting body aluminium foil；Oven drying is transferred them to, then by cold pressing, obtains anode pole piece.
2, prepared by cathode pole piece: taking degree of graphitization is that 94% artificial plumbago negative pole active material sample (uses X-ray diffraction Instrument is measured).By artificial plumbago negative pole active material, sodium carboxymethylcellulose (thickener), SBR (butadiene-styrene rubber binder) 97:1.2:1.8 is mixed in mass ratio, and deionized water is added, and obtains uniform negative electrode slurry under de-airing mixer effect； Negative electrode slurry is coated uniformly on negative current collector copper foil；Oven drying is transferred them to, then by cold pressing, obtains cathode Coating layer of active substance compacted density is 1.5g/cm3Cathode pole piece.
Here compacted density measures by the following method: coated pole piece being carried out tabletting on roll squeezer, is adjusted Rolling pressure or roll gap gap, the pole piece thickness after testing pole piece roll-in.
Compacted density=(unit area pole piece weight-unit area afflux body weight)/(pole piece single side thickness-collector Thickness)
3, electrolyte quota: by ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) according to volume It is mixed than 3:6:1, then by sufficiently dry lithium salts LiPF6Mixed organic solvents are dissolved according to the ratio of 1mol/L In, it is configured to electrolyte.
4, isolation film: 12 microns of PP/PE composite isolated film
5, prepared by full battery: above-mentioned positive plate, isolation film, negative electrode tab being folded in order, isolation film is made to be in positive and negative electrode Play the role of isolation between piece, then winding obtains naked battery core；Naked battery core is placed in outer packing shell, is prepared above-mentioned Electrolyte is injected into the naked battery core after drying, by processes such as Vacuum Package, standing, chemical conversion, shapings, obtains lithium-ion electric Pond.
Embodiment 2
Battery core preparation section is same as Example 1, and difference is: negative electrode active on cathode pole piece obtained in step 2 The compacted density of matter coatings is 1.6g/cm3。
Embodiment 3
Battery core preparation section is same as Example 1, and difference is: negative electrode active on cathode pole piece obtained in step 2 The compacted density of matter coatings is 1.7g/cm3。
Embodiment 4
Battery core preparation section is same as Example 1, and difference is: negative electrode active on cathode pole piece obtained in step 2 The compacted density of matter coatings is 1.8g/cm3。
Embodiment 5
Battery core preparation section is same as Example 3, and difference is: the graphite for the negative electrode active material selected in step 2 Change degree is 92%.
Embodiment 6
Battery core preparation section is same as Example 3, and difference is: the graphite for the negative electrode active material selected in step 2 Change degree is 95%.
Embodiment 7
Battery core preparation section is same as Example 3, and difference is: the graphite for the negative electrode active material selected in step 2 Change degree is 97%.
Embodiment 8
Battery core preparation section is same as Example 3, and difference is: the positive electrode active materials selected in step 1 are LiNi0.5Co0.25Mn0.25O2。
Embodiment 9
Battery core preparation section is same as Example 3, and difference is: the positive electrode active materials selected in step 1 are LiNi1/3Co1/3Mn1/3O2。
Embodiment 10
Battery core preparation section is same as Example 3, and difference is: the positive electrode active materials selected in step 1 are LiNi0.8Co0.1Mn0.1O2。
Embodiment 11
Battery core preparation section is same as Example 3, and difference is: the positive electrode active materials selected in step 1 are containing cladding Layer, the element ti containing cladding.
Embodiment 12
Battery core preparation section is same as Example 3, and difference is: the positive electrode active materials selected in step 1 are containing cladding Layer coats element ti, doped chemical Al.
Comparative example 1
Preparation method is same as Example 1, and difference is: negative electrode active material on cathode pole piece obtained in step 2 The compacted density of coating is 1.4g/cm3。
Comparative example 2
Preparation method is same as Example 1, and difference is: negative electrode active material on cathode pole piece obtained in step 2 The compacted density of coating is 1.9g/cm3。
Comparative example 3
Preparation method is same as Example 3, and difference is: the degree of graphitization for the negative electrode active material selected in step 2 It is 88%.
Comparative example 4
Preparation method is same as Example 3, and difference is: the degree of graphitization for the negative electrode active material selected in step 2 It is 99%.
The test of full battery cycle performance:
The full battery cycle performance test of each embodiment and comparative example carries out as follows:
In 25 DEG C of environment, first time charging and discharging are carried out, (i.e. bleed off the electricity of theoretical capacity in 1h completely in 1.0C Flow valuve) charging current under carry out constant current and constant-voltage charge, until upper limit voltage is 4.2V, then under the discharge current of 1.0C Constant-current discharge is carried out, until final voltage is 2.8V, the discharge capacity that record recycles for the first time；Lasting charge and discharge are then carried out to follow Ring.
Circulation volume conservation rate=(discharge capacity of n-th circulation/discharge capacity recycled for the first time) × 100
Analyse the test of lithium multiplying power
Full battery analyses the test of lithium high rate performance:
In 25 DEG C of environment, charge-discharge test is carried out, 1.0C (i.e. bleeding off the current value of theoretical capacity in 1h completely) Electric discharge electricity electric current under carry out constant-current discharge, until voltage be 2.8V.Then under the charging current of 1.0C constant-current charge to electricity Pressure is 4.2V, and continuing constant-voltage charge to electric current is 0.05C, and battery is fully charged state at this time.After the battery core completely filled is stood 5min, Constant-current discharge is the actual capacity under the 1.0C of battery core to 2.8V, discharge capacity at this time under the discharge current of 1.0C, is denoted as C0。
Then by battery core, in xC0 constant-current charge to 4.2V, then constant-voltage charge to electric current is 0.05C0, stands 5min, tears open It solves battery core observing interface and analyses lithium situation, adjust rate of charge, until there is analysis lithium, determine analysis lithium multiplying power.
The test of battery core energy density
In 25 DEG C of environment, charge-discharge test is carried out, 1.0C (i.e. bleeding off the current value of theoretical capacity in 1h completely) Electric discharge electricity electric current under carry out constant-current discharge, until voltage be 2.8V.Then under the charging current of 1.0C constant-current charge to electricity Pressure is 4.2V, and continuing constant-voltage charge to electric current is 0.05C, and battery is fully charged state at this time.After the battery core completely filled is stood 5min, Constant-current discharge is the actual capacity under the 1.0C of battery core to 2.8V, discharge capacity at this time under the discharge current of 1.0C, is denoted as C0。
Battery core energy density=C0 × plateau potential/battery core weight
The machined parameters of each embodiment and comparative example, the performance parameter of material and battery performance are summarized in table 1 and table 2。
Table 1
Comparative example Roll gap (mm) Pressure (ton)
Embodiment 1 0.73 23
Embodiment 2 0.65 30
Embodiment 3 0.59 39
Embodiment 4 0.52 52
Embodiment 5 0.57 43
Embodiment 6 0.60 38
Embodiment 7 0.62 36
Embodiment 8 0.59 39
Embodiment 9 0.59 39
Embodiment 10 0.59 39
Embodiment 11 0.59 39
Embodiment 12 0.59 39
Comparative example 1 0.81 18
Comparative example 2 0.41 60
Comparative example 3 0.49 65
Comparative example 4 0.70 26
Table 2
Test data analyzer:
1, it analyzes known to embodiment 1-4, comparative example 1-2:
When the compacted density of negative electrode active material coating is not present invention provide that when in range, the analysis lithium multiplying power of battery and 500 times circulation volume conservation rate significantly reduces.Embodiment 1-4 is analyzed it is found that working as one timing of degree of graphitization of negative electrode material, battery 500 circulation volume conservation rates have the tendency that improving with the increase of the compacted density of negative electrode active material coating.
2, embodiment 3,5-7, comparative example 3-4 is analyzed to know:
When the degree of graphitization of negative electrode material is not present invention provide that when in range, cycle performance of battery and analysis lithium are obviously disliked Change.Embodiment 3,5-7 are analyzed it is found that working as one timing of compacted density of negative electrode active material coating, degree of graphitization is higher, battery core Energy density is higher.
3, it analyzes known to embodiment 3,11-12:
After being doped and/or coating to positive electrode, it can further improve battery analysis lithium multiplying power and 500 circulations are held Measure conservation rate.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.

Claims (10)

1. a kind of lithium ion secondary battery, including anode pole piece, cathode pole piece, isolation film and electrolyte；
Wherein the anode pole piece includes plus plate current-collecting body and positive active material coating, and the positive active material coating includes General formula is LixNiaCobMcO2Positive electrode active materials, wherein M is selected from least one of Mn, Al, 0.95≤x≤1.2,0 < a 1,0 < b < of <, 1,0 < c < 1 and a+b+c=1；And
The cathode pole piece includes negative current collector and negative electrode active material coating, and the negative electrode active material coating includes graphite Change degree is the graphitized carbon material of 92%-97% as negative electrode active material, and the compacting of the negative electrode active material coating is close Degree is 1.5-1.8g/cm3。
2. lithium ion secondary battery according to claim 1, the positive electrode active materials are selected from LiNi0.33Co0.33Mn0.33O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.5Co0.25Mn0.25O2、LiNi0.6Co0.2Mn0.2O2、 LiNi0.8Co0.1Mn0.1O2、LiNi0.85Co0.1Mn0.05O2、LiNi0.8Co0.15Al0.05O2At least one of.
3. -2 described in any item lithium ion secondary batteries according to claim 1, the positive electrode active materials there are doped chemical, The doped chemical is selected from least one of Al, Zr, Ti, B, Mg, V, Cr, F.
4. there is packet in the surface of lithium ion secondary battery according to claim 1-3, the positive electrode active materials Coating, the clad contain at least one of Al, Zr, Ti, B element.
5. lithium ion secondary battery according to claim 1, the compacted density of the negative electrode active material coating is 1.6- 1.7g/cm3。
6. lithium ion secondary battery according to claim 1, the degree of graphitization of the negative electrode active material is 93%- 95%.
7. lithium ion secondary battery according to claim 1, there are clad, the cladding in the negative electrode active material surface Layer is amorphous carbon.
8. lithium ion secondary battery according to claim 7, the amorphous carbon be by selected from selected from coal tar pitch and petroleum asphalt, Mesophase pitch, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, gathers epoxy resin Obtained from the charing of at least one of ethylene oxide, Kynoar, acrylic resin and polyacrylonitrile material.
9. lithium ion secondary battery according to claim 7, the amorphous carbon is total relative to the negative electrode active material The content of weight is 2-13%, preferably 2-10%.
10. the weight of -9 described in any item lithium ion secondary batteries according to claim 1, the positive electrode active materials accounts for anode The 92%-98% of coating layer of active substance, the weight of the negative electrode active material account for the 92%-98% of negative electrode active material coating.
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