CN105355889B - A kind of high voltage high multiplying power lithium ion battery - Google Patents

A kind of high voltage high multiplying power lithium ion battery Download PDF

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CN105355889B
CN105355889B CN201510853782.8A CN201510853782A CN105355889B CN 105355889 B CN105355889 B CN 105355889B CN 201510853782 A CN201510853782 A CN 201510853782A CN 105355889 B CN105355889 B CN 105355889B
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cobalt acid
acid lithium
lithium
ion battery
battery
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CN105355889A (en
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王宏宇
李君侠
杨洪
李峰
何显峰
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XI'AN SEFU ENERGY TECHNOLOGY Co Ltd
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XI'AN SEFU ENERGY TECHNOLOGY Co Ltd
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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

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  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of high voltage high multiplying power lithium ion battery, including positive plate, negative plate, barrier film, electrolyte, positive pole ear, negative lug and pack case, the positive plate is that the anode sizing agent containing positive active material is coated on into aluminium foil two sides and is made, and the positive active material is D50Particle diameter is 4.0 μm~12.0 μm, specific surface area 0.5m2/ g~1.2m2/ g modification cobalt acid lithium.The battery of the present invention possesses high-rate discharge capacity and excellent circulation ability, compared to the conventional lithium-ion battery that charge cutoff voltage is 4.35V, the battery of the present invention can support 3C~45C heavy-current discharges, electric discharge ratio is more than 90%, circulated under high voltages using 3C~45C high currents, service life was up to more than 400 weeks.

Description

A kind of high voltage high multiplying power lithium ion battery
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of high voltage high multiplying power lithium ion battery.
Background technology
At present, lithium ion battery possesses the advantages such as high operating voltage, in light weight, long lifespan higher than energy, self discharge be low, It is widely used in all kinds of electronic products, electric tool and model toy etc..The operating current of conventional electrical equipment is small, when standby Between it is long, conventional type lithium ion battery can meet its requirement.And for model toys such as car mould, model plane, ship model and electronic The electrical equipments such as instrument, need lithium ion battery persistently to provide high current in the course of the work, to meet its high-power output It is required that this requirement uses high multiplying power lithium ion battery manufacturing technology.The patent of Application No. 200910021703.1 is to such product Carried out explanation.But with the development of technology and the raising of user's request, higher work(is proposed to rate lithium ion battery Rate output requires.
It is difficult the power capability for fundamentally lifting battery to carry out process structure merely on the original basis to improve.It is logical The charge cutoff voltage for improving battery is crossed, the energy of battery in unit volume can be improved, and then realizes that high-energy exports.As The stratiform cobalt acid lithium material of current lithium ion battery main flow positive electrode, when charge cutoff voltage is more than 4.2V, more than 50% Li+Deviate from from stratiform cobalt acid lithium lattice, causing stratiform cobalt acid lithium material to occur, crystal formation changes and structure presence is caved in Hidden danger, performance, service life and the security of battery are greatly reduced.Need to be modified cobalt acid lithium material, improve high electricity Press the stability of material under state.The such production of the patent of Application No. 200580017392.1 and Application No. 201210078203.3 Product carried out explanation, but modified cobalt acid lithium material required by its patent and lithium ion battery are only applicable to conventional type lithium-ion electric Pond, i.e. operating current are less than 1C.When operating current is more than 1C, the modification cobalt acid lithium required by its patent is because of doping metals and bag The electric conductivity of coating in itself, leads to not meet heavy-current discharge requirement, used metal-doped and rich lithium not as cobalt acid lithium Stratiform transition metal oxide Li2MO3There are still structure under high voltage, high-multiplying power discharge for the modified cobalt acid lithium material of cladding Destabilizing factor, long-term high rate cyclic, cell performance decay is quickly.
Therefore, to realize the requirement of more power output, it is necessary to provide it is a kind of under high voltages, realize that high magnification follows Ring, and the lithium ion battery of stable performance.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the deficiencies in the prior art, there is provided a kind of high voltage high power Rate lithium ion battery.The battery possesses high-rate discharge capacity and excellent circulation ability, is compared to charge cutoff voltage 4.35V conventional lithium-ion battery, the battery can support 3C~45C heavy-current discharges, and electric discharge ratio is more than 90%, in high electricity Pressure is circulated using 3C~45C high currents, and service life was up to more than 400 weeks.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of high voltage high multiplying power lithium ion battery, Including positive plate, negative plate, barrier film, electrolyte, positive pole ear, negative lug and pack case, the positive plate is by containing positive pole The anode sizing agent of active material is coated on aluminium foil two sides and is made, it is characterised in that the high voltage high multiplying power lithium ion battery Charge cutoff voltage be 4.35V, 3C~45C current discharges can be supported；The positive active material is D50Particle diameter be 4.0 μm~ 12.0 μm, specific surface area 0.5m2/ g~1.2m2/ g modification cobalt acid lithium；
The preparation method of the modified cobalt acid lithium comprises the following steps：
Step 1: cobalt chloride and metallic element M sulfate are configured into metal ion total concentration with deionized water being 0.5mol/L~1.5mol/L mixed solution, the pH value of the mixed solution is then adjusted with sodium hydroxide solution to 9~12, Centrifuge, precipitated after stirring 2h~6h；The precipitation is first used into absolute ethyl alcohol supersound washing, then washed with deionized water ultrasound Wash to neutrality, being deposited at 70 DEG C~90 DEG C after deionized water supersound washing is dried into 6h~12h, metal ion is obtained and mixes Miscellaneous presoma MyCo1-y(OH)2, wherein y=0.0001~0.1, the one or more in M Al, Cr, Ni and Mn；Again by described in Metal ion mixing presoma MyCo1-y(OH)2With lithium carbonate according to Li:Co=(1.05~1.1)：1 mixed in molar ratio, 5h~10h is calcined under conditions of 500 DEG C~1000 DEG C, obtains metal ion mixing cobalt acid lithium Li (MyCo1-y)O2；
Step 2: by metal ion mixing cobalt acid lithium Li (M described in organic carbon source and step 1yCo1-y)O2According to Li:C =1:Be placed in after the mixed in molar ratio of (3~5) in ptfe autoclave, using deionized water as reaction medium, 160 DEG C~ 24h~48h is reacted at 220 DEG C, reacted material is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing To neutrality, the material after deionized water supersound washing is dried into 6h~12h at 70 DEG C~90 DEG C, obtains carbon coating cobalt acid Lithium；The organic carbon source is the one or more in urea, grape sugar and starch；
Step 3: using absolute ethyl alcohol as decentralized medium, by external coating oxide, surfactant, filler and step Carbon coating cobalt acid lithium described in two is uniformly dispersed to obtain mixture, then the mixture is heated to concentration at 60 DEG C~80 DEG C Obtain gel, by the gel at 60 DEG C~200 DEG C heat resolve 1h~4h, then at 500 DEG C~1000 DEG C calcine 4h~ 9h, it will be sieved after the gel abrasive after calcining, obtain being modified cobalt acid lithium；The quality of the carbon coating cobalt acid lithium accounts for external coating oxygen Compound, surfactant, the 65%~88.5% of filler and carbon coating cobalt acid lithium gross mass, the quality of external coating oxide Account for external coating oxide, surfactant, filler and carbon coating cobalt acid lithium gross mass 10%~30%, surfactant Quality account for the 1%~10% of external coating oxide, surfactant, filler and carbon coating cobalt acid lithium gross mass, filling The quality of thing accounts for the 0.5%~5% of external coating oxide, surfactant, filler and carbon coating cobalt acid lithium gross mass；Institute It is SiO to state external coating oxide2、ZrO2And CeO2In one or more, surfactant is sapn and/or tween, filling Thing is polyurethanes.
A kind of above-mentioned high voltage high multiplying power lithium ion battery, it is characterised in that y=0.05~0.1 described in step 1.
Above-mentioned a kind of high voltage high multiplying power lithium ion battery, it is characterised in that contain ionic liquid in the electrolyte Additive, the ion liquid addictive are difluoro (oxalic acid) lithium borate, N- methyl-N- acetoxyl groups-bis- (trifluoro methylsulfonyls Base) imines piperidines, 1- ethyl -3- methyl-bis- (fluorosulfonyl) imine imidazoles and N, N '-(trifluoro of diethyl -3- methylpyrazoles two Sulfonyloxy methyl) one or more in imines.
A kind of above-mentioned high voltage high multiplying power lithium ion battery, it is characterised in that the electrolyte intermediate ion liquid addition The weight/mass percentage composition of agent is 0.5%~3.0%.
Above-mentioned a kind of high voltage high multiplying power lithium ion battery, it is characterised in that the negative plate is by containing negative electrode active The cathode size of material is coated on copper foil two sides and is made, and the two-sided deposited charge level density of negative plate is 60g/m2~180g/m2, pressure Real density is 1.3g/m3~1.6g/m3。
Above-mentioned a kind of high voltage high multiplying power lithium ion battery, it is characterised in that the two-sided deposited charge level of the positive plate is close Spend for 100g/m2~300g/m2, compacted density 3.4g/m3~3.9g/m3。
The present invention has advantages below compared with prior art：
1st, the present invention is modified to cobalt acid lithium, prepares metal ion mixing cobalt acid lithium using coprecipitation first, is adulterated Metal ion stabilizes the layer structure of cobalt acid lithium, electric conductivity is improved, so as to improve the cycle performance of battery；Then hydro-thermal is used Method prepares carbon coating cobalt acid lithium, and cladding processing reduces cobalt acid lithium and the contact area of electrolyte, reduces in material cobalt in electricity The dissolving in liquid is solved, can effectively prevent structure collapses, improves cycle performance of the battery under high-voltage state, security performance, big Current discharge capacity and high rate performance；Modified cobalt acid lithium, external coating oxide and carbon bag are finally prepared using liquid phase synthesizing method Cover cobalt acid lithium and form core shell structure after high-temperature calcination removes carbon-coating, filler decomposes completely in high-temperature burning process, and it is former Originally the space occupied forms hole.Prepared modified cobalt acid lithium material, its spherical clad structure not only added contact area but also Material structure stability is improved, pore structure provides abundant specific surface area so that lithium ion can quickly be embedded in/take off Go out.
2nd, the present invention preferably uses ion liquid addictive in the electrolytic solution, and there is ionic liquid vapour pressure to be approximately equal to Zero, it is non-volatile, it is nonflammable explosive, it is not oxidizable, the characteristics of being stabilized below 300 DEG C, significantly increase electrolyte The security of system, while to many inorganic salts and organic matter with good dissolubility and with the electrochemical window more than 3V Mouthful.Currently preferred several ionic liquids, its electrochemical window greatly improve lithium ion battery in high electricity in 5V~6V Press the stability and storge quality under state.
3rd, battery charge cutoff voltage of the invention is 4.35V, compared with charge cutoff voltage is 4.2V lithium ion batteries, Positive active material gram volume plays lifting 10%~15%, identical size cell capacity boost 9%~11%.
4th, battery of the invention possesses high-rate discharge capacity, compared to the common lithium-ion that charge cutoff voltage is 4.35V Battery, battery of the present invention can support 3C~45C heavy-current discharges, and electric discharge ratio is more than 90%.
5th, battery of the invention possesses excellent circulation ability, is circulated under high voltages using 3C~45C high currents, Service life was up to more than 400 weeks.And common high-multiplying-power battery circulates on this condition, quickly, service life is or not capacity attenuation Foot 100 weeks.
In summary, the present invention breaks through the technical deficiency of existing high-multiplying-power battery and high-voltage battery, not only significantly carries The high capacity density of battery, while realize high-multiplying power discharge and high-voltage discharge platform.The lithium ion battery of the present invention, can Under the conditions of in charge cutoff voltage as 4.35V, 3C~45C high rate cyclics are carried out for a long time, battery performance is stable, service life Up to more than 400 weeks.
With reference to the accompanying drawings and examples, technical solution of the present invention is described in further detail.
Brief description of the drawings
Fig. 1 is the 1C discharge curves of the high voltage high multiplying power lithium ion battery difference discharge range of the embodiment of the present invention 6.
Fig. 2 is the lithium ion battery of comparative example 1, comparative example 3 and the embodiment of the present invention 6 in 4.35V~3.0V sections Circulation curve map.
Embodiment
Embodiment 1
Prepare modified cobalt acid lithium：
Step 1: cobalt chloride and chromium sulfate are configured to the mixing that metal ion total concentration is 1.0mol/L with deionized water Solution, the pH value of the mixed solution is then adjusted with sodium hydroxide solution to 11, centrifuges, is precipitated after stirring 6h；By institute State precipitation and first use absolute ethyl alcohol supersound washing, will be through deionized water supersound washing then with deionized water supersound washing to neutrality 12h is dried in being deposited at 80 DEG C afterwards, obtains metal ion mixing presoma Cr0.1Co0.9(OH)2；Again by the metal ion Adulterate presoma Cr0.1Co0.9(OH)2With lithium carbonate according to Li:Co=1.05：1 mixed in molar ratio, under conditions of 600 DEG C 9h is calcined, obtains metal ion mixing cobalt acid lithium Li (Cr0.1Co0.9)O2；
Step 2: by metal ion mixing cobalt acid lithium Li (Cr described in organic carbon source urea and step 10.1Co0.9)O2Press According to Li:C=1:It is placed in after 3 mixed in molar ratio in ptfe autoclave, using deionized water as reaction medium, at 160 DEG C Lower reaction 48h, reacted material is first used into absolute ethyl alcohol supersound washing, will then with deionized water supersound washing to neutrality Material after deionized water supersound washing dries 12h at 80 DEG C, obtains carbon coating cobalt acid lithium；
Step 3: using absolute ethyl alcohol as decentralized medium, by external coating oxide, surfactant, filler and step Carbon coating cobalt acid lithium described in two is uniformly dispersed to obtain mixture, then the mixture is heated at 70 DEG C be concentrated to give it is solidifying Glue, by the gel at 150 DEG C heat resolve 2h, then calcine 9h at 600 DEG C, will be sieved after the gel abrasive after calcining, Obtain D50Particle diameter is 4.0 μm and specific surface area is 1.2m2/ g modification cobalt acid lithium；The carbon coating cobalt acid lithium, external coating oxygen The quality of compound, surfactant and filler accounts for external coating oxide, surfactant, filler and carbon coating cobalt respectively 85%, 10%, 2.5% and the 2.5% of sour lithium gross mass；The external coating oxide is ZrO2, surfactant is tween 80, filler is polyurethanes.
Embodiment 2
Prepare modified cobalt acid lithium：
Step 1: cobalt chloride and aluminum sulfate are configured to the mixing that metal ion total concentration is 1.0mol/L with deionized water Solution, the pH value of the mixed solution is then adjusted with sodium hydroxide solution to 9, centrifuges, is precipitated after stirring 4h；By described in Precipitation first uses absolute ethyl alcohol supersound washing, will be after deionized water supersound washing then with deionized water supersound washing to neutrality Be deposited at 70 DEG C dry 10h, obtain metal ion mixing precursor A l0.05Co0.95(OH)2；The metal ion is mixed again Miscellaneous precursor A l0.05Co0.95(OH)2With lithium carbonate according to Li:Co=1.08：1 mixed in molar ratio, roasted under conditions of 800 DEG C 6h is burnt, obtains metal ion mixing cobalt acid lithium Li (Al0.05Co0.95)O2；
Step 2: by metal ion mixing cobalt acid lithium Li (Al described in organic carbon source glucose and step 10.05Co0.95) O2According to Li:C=1:It is placed in after 3 mixed in molar ratio in ptfe autoclave, using deionized water as reaction medium, 40h is reacted at 200 DEG C, reacted material is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing into Property, the material after deionized water supersound washing is dried into 8h at 80 DEG C, obtains carbon coating cobalt acid lithium；
Step 3: using absolute ethyl alcohol as decentralized medium, by external coating oxide, surfactant, filler and step Carbon coating cobalt acid lithium described in two is uniformly dispersed to obtain mixture, then the mixture is heated at 80 DEG C be concentrated to give it is solidifying Glue, by the gel at 120 DEG C heat resolve 3h, then calcine 6h at 800 DEG C, will be sieved after the gel abrasive after calcining, Obtain D50Particle diameter is 6.0 μm and specific surface area is 0.85m2/ g modification cobalt acid lithium；The carbon coating cobalt acid lithium, external coating oxygen The quality of compound, surfactant and filler accounts for external coating oxide, surfactant, filler and carbon coating cobalt respectively 70%, 20%, 5% and the 5% of sour lithium gross mass；The external coating oxide is SiO2, surfactant is sorbester p18, is filled out It is polyurethanes to fill thing.
Embodiment 3
Prepare modified cobalt acid lithium：
Step 1: cobalt chloride and nickel sulfate are configured to the mixing that metal ion total concentration is 1.5mol/L with deionized water Solution, the pH value of the mixed solution is then adjusted with sodium hydroxide solution to 12, centrifuges, is precipitated after stirring 2h；By institute State precipitation and first use absolute ethyl alcohol supersound washing, will be through deionized water supersound washing then with deionized water supersound washing to neutrality 10h is dried in being deposited at 70 DEG C afterwards, obtains metal ion mixing presoma Ni0.0001Co0.9999(OH)2；Again by the metal Ion doping presoma Ni0.0001Co0.9999(OH)2With lithium carbonate according to Li:Co=1.1：1 mixed in molar ratio, at 1000 DEG C Under conditions of be calcined 5h, obtain metal ion mixing cobalt acid lithium Li (Ni0.0001Co0.9999)O2；
Step 2: by metal ion mixing cobalt acid lithium Li (Ni described in organic carbon source urea and step 10.0001Co0.9999) O2According to Li:C=1:It is placed in after 4 mixed in molar ratio in ptfe autoclave, using deionized water as reaction medium, 24h is reacted at 220 DEG C, reacted material is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing into Property, the material after deionized water supersound washing is dried into 10h at 70 DEG C, obtains carbon coating cobalt acid lithium；
Step 3: using absolute ethyl alcohol as decentralized medium, by external coating oxide, surfactant, filler and step Carbon coating cobalt acid lithium described in two is uniformly dispersed to obtain mixture, then the mixture is heated at 80 DEG C be concentrated to give it is solidifying Glue, by the gel at 200 DEG C heat resolve 1h, then calcine 4h at 1000 DEG C, will be sieved after the gel abrasive after calcining, Obtain D50Particle diameter is 6.5 μm and specific surface area is 0.59m2/ g modification cobalt acid lithium；The carbon coating cobalt acid lithium, external coating oxygen The quality of compound, surfactant and filler accounts for external coating oxide, surfactant, filler and carbon coating cobalt respectively 88.5%, 10%, 1% and the 0.5% of sour lithium gross mass；The external coating oxide is CeO2, surfactant is tween 80 and sorbester p18 (mass ratio 1:1), filler is polyurethanes.
Embodiment 4
Prepare modified cobalt acid lithium：
Step 1: cobalt chloride and metallic element M sulfate are configured into metal ion total concentration with deionized water being 0.5mol/L mixed solution, the pH value of the mixed solution is then adjusted with sodium hydroxide solution to 10, is centrifuged after stirring 4h, Precipitated；The precipitation is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing to neutrality, will through go from Being deposited at 90 DEG C after sub- water supersound washing dries 6h, obtains metal ion mixing presoma M0.08Co0.92(OH)2, metal member Plain M is Al and Cr, i.e., metallic element M sulfate is that (wherein Al and Cr mol ratio are 1 for aluminum sulfate and chromium sulfate:1)；Again will The metal ion mixing presoma M0.08Co0.92(OH)2With lithium carbonate according to Li:Co=1.05：1 mixed in molar ratio, 10h is calcined under conditions of 500 DEG C, obtains metal ion mixing cobalt acid lithium Li (M0.08Co0.92)O2；
Step 2: by metal ion mixing cobalt acid lithium Li (M described in organic carbon source and step 10.08Co0.92)O2According to Li:C=1:It is placed in after 5 mixed in molar ratio in ptfe autoclave, using deionized water as reaction medium, at 180 DEG C 36h is reacted, reacted material is first used into absolute ethyl alcohol supersound washing, will be through then with deionized water supersound washing to neutrality Material after deionized water supersound washing dries 6h at 90 DEG C, obtains carbon coating cobalt acid lithium, the organic carbon source is glucose (mol ratio of the carbon in carbon and starch in glucose is 1 with starch:1)；
Step 3: using absolute ethyl alcohol as decentralized medium, by external coating oxide, surfactant, filler and step Carbon coating cobalt acid lithium described in two is uniformly dispersed to obtain mixture, then the mixture is heated at 60 DEG C be concentrated to give it is solidifying Glue, by the gel at 60 DEG C heat resolve 4h, then calcine 9h at 500 DEG C, will sieve, obtain after the gel abrasive after calcining To D50Particle diameter is 12.0 μm and specific surface area is 0.5m2/ g modification cobalt acid lithium；The carbon coating cobalt acid lithium, external coating oxidation The quality of thing, surfactant and filler accounts for external coating oxide, surfactant, filler and carbon coating cobalt acid respectively 65%, 30%, 3.5% and the 1.5% of lithium gross mass；The external coating oxide is SiO2And ZrO2(Si and Zr mol ratio For 1:2), surfactant is Tween 80 and sorbester p18 (mass ratio 1:1), filler is polyurethanes.
Embodiment 5
Prepare modified cobalt acid lithium：
Step 1: cobalt chloride and metallic element M sulfate are configured into metal ion total concentration with deionized water being 0.5mol/L mixed solution, the pH value of the mixed solution is then adjusted with sodium hydroxide solution to 10, is centrifuged after stirring 4h, Precipitated；The precipitation is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing to neutrality, will through go from Being deposited at 90 DEG C after sub- water supersound washing dries 6h, obtains metal ion mixing presoma M0.1Co0.9(OH)2, metal member Plain M is Al, Cr, Ni and Mn, i.e., metallic element M sulfate be aluminum sulfate, chromium sulfate, nickel sulfate and manganese sulfate (wherein Al, Cr, Ni and Mn mol ratio are 1:1:2:1)；Again by the metal ion mixing presoma M0.1Co0.9(OH)2Pressed with lithium carbonate According to Li:Co=1.05：1 mixed in molar ratio, 10h is calcined under conditions of 500 DEG C, obtains metal ion mixing cobalt acid lithium Li (M0.1Co0.9)O2；
Step 2: by metal ion mixing cobalt acid lithium Li (M described in organic carbon source and step 10.1Co0.9)O2According to Li: C=1:It is placed in ptfe autoclave after 5 mixed in molar ratio, using deionized water as reaction medium, is reacted at 180 DEG C 36h, reacted material is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing to neutrality, will through go from Material after sub- water supersound washing dries 6h at 90 DEG C, obtains carbon coating cobalt acid lithium, and the organic carbon source is urea, glucose (mol ratio of the carbon in the carbon and starch in carbon, glucose in urea is 1 with starch:2:3)；
Step 3: using absolute ethyl alcohol as decentralized medium, by external coating oxide, surfactant, filler and step Carbon coating cobalt acid lithium described in two is uniformly dispersed to obtain mixture, then the mixture is heated at 60 DEG C be concentrated to give it is solidifying Glue, by the gel at 60 DEG C heat resolve 4h, then calcine 9h at 500 DEG C, will sieve, obtain after the gel abrasive after calcining To D50Particle diameter is 8.5 μm and specific surface area is 0.68m2/ g modification cobalt acid lithium；The carbon coating cobalt acid lithium, external coating oxidation The quality of thing, surfactant and filler accounts for external coating oxide, surfactant, filler and carbon coating cobalt acid respectively 70%, 15%, 10% and the 5% of lithium gross mass；The external coating oxide is SiO2、ZrO2And CeO2(Si, Zr and Ce's Mol ratio is 1:1:3), surfactant is Tween 80, and filler is polyurethanes.
Embodiment 6
Using capacity as 2500mAh, thickness 8.0mm, width 34mm, length are 96mm high voltage high multiplying power lithium ion Illustrated exemplified by the manufacturing process of battery, specific implementation process is as follows：
The preparation of anode sizing agent：With N- dimethyl pyrrolidones (NMP) for solvent, positive active material is that embodiment 1 is made Standby D50It is 1.2m for 4.0 μm and specific surface area2/ g modification cobalt acid lithium, conductive agent are super conductive black (Super-P), are glued It is Kynoar (PVDF) to connect agent.Mass ratio is used in the present embodiment：Modified cobalt acid lithium:Super-P:PVDF:NMP= 96.2:2:1.8:65.Cobalt acid lithium and Super-P pre-dispersed 1h~2h in batch mixer will be first modified, makes conductive agent dispersed On modified cobalt acid lithium surface, cathode mix is obtained；Then PVDF is added in NMP, stirs 2h~4h, PVDF is prepared Glue；Cathode mix is added in three times in above-mentioned PVDF glues, vacuumizes de-bubbled after stirring 5h~8h, obtain positive pole Slurry.
The making of anode pole piece：The anode sizing agent prepared is coated on collector utter misery aluminium foil, two-sided deposited charge level is close Spend for 154g/m2, compacted density 3.55g/m3, the aluminium foil after coating is to be assembled after drying, roll-in and punching, completes positive pole The making of piece.
The preparation of cathode size：With deionized water (H2O) it is solvent, negative electrode active material is carbonaceous mesophase spherules (MCMB), conductive agent is super conductive black (Super-P), and bonding agent is butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC) composition.Mass ratio is used in the present embodiment：MCMB:Super-P:SBR:CMC:H2O=94.6:2:2:1.4: 150.First by MCMB and Super-P in batch mixer pre-dispersed 2h~3h, conductive agent is dispersed in MCMB surfaces, born Pole mixture；Then CMC is added in deionized water, stirs 3h~4h, prepare the CMC aqueous solution；It is divided to two by negative electrode mix It is secondary to add in the above-mentioned CMC aqueous solution, SBR is added after stirring 6h~10h, continues to vacuumize de-bubbled after stirring 1h~2h, obtains Cathode size.
The making of cathode pole piece：The cathode size prepared is coated on the copper foil of affluxion body of roughening, two-sided deposited charge level Density is in 86g/m2, compacted density 1.35g/m3, coating pole piece is to be assembled after drying, roll-in and punching, completes negative plate Make.
The preparation of electrolyte：Lithium salts is lithium hexafluoro phosphate (LiPF6), solvent is ethylene carbonate (EC), dimethyl carbonate (DMC), the quaternary mixed liquor of methyl ethyl carbonate (EMC) and diethyl carbonate (DEC), mass ratio EC:DMC:EMC:DEC=3: 4:2:1, ion liquid addictive is N- methyl-N- acetoxyl groups-bis- (trifyl) imines piperidines ([MMEPip] [TFSI]) and 1- ethyl -3- methyl-bis- (fluorosulfonyl) imine imidazoles ([C2Mim] [FSA]), the concentration of lithium salts in electrolyte For 1.5mol/L, the mass concentration of [MMEPip] [TFSI] is 1.0%, [C2Mim] [FSA] mass concentration be 0.5%.
The making of battery before chemical conversion：By the positive and negative plate being punched and barrier film by barrier film, negative pole, barrier film, positive pole, barrier film Stacked gradually with the order of negative pole and be combined into battery core, (individual layer Jing Guo ceramic coated gathers its septation using ceramic coating membrane Propylene barrier film).The battery core being combined into carries out ultrasonic wave using aluminium pole ears (positive pole ear) and copper nickel plating lug (negative lug) Welding；The battery core welded is put into aluminum-plastic packaged shell and once encapsulated；By the battery core that once encapsulates in temperature 80 DEG C~85 DEG C, 24h is toasted under conditions of vacuum≤- 0.08MPa；The above-mentioned electrolysis prepared is injected to the battery core toasted Liquid；It is to be changed after battery core standing 24h~48h after fluid injection.
The chemical conversion of battery：Chemical conversion uses 0.05C constant current charge 2h, stands 10min, 0.2C constant current charges 2h；Then Complete pumping and secondary encapsulation；4.35V, 1C constant current discharges to 3.0V, 1C perseverances are finally charged to using 1C constant current constant voltage patterns Stream constant voltage mode charges to 3.9V, completes chemical conversion.
Comparative example 1
With D50It is 0.53m for 5.2 μm and specific surface area2/ g common high magnification spherical lithium cobalt is as positive electrode active material Matter, it be 2500mAh, thickness 8.0mm, width 34mm to make capacity according to the method for embodiment 6, length for 96mm lithium from Sub- battery.
Comparative example 2
With D50It is 0.22m for 9.3 μm and specific surface area2/ g Li2MnO3The high voltage LiCoO of cladding2As positive-active Material, it is 2500mAh, thickness 8.0mm, width 34mm to make capacity according to the method for embodiment 6, and length is 96mm lithium Ion battery.
Comparative example 3
Ion liquid addictive is not added in the electrolytic solution, and lithium ion battery is made according to the method for embodiment 6.
To the battery of embodiment 6, comparative example 1 and comparative example 2 in 4.2V~3.0V and 4.35V~3.0V Liang Zhong discharge and recharges area Between under 1C capacity and positive pole 1C gram volume situations contrasted, be shown in Table 1.
The battery capacity contrast table that 1 different positive electrode active materials of table make
As it can be seen from table 1 charging to 4.35V to cobalt acid lithium material, the capacity and positive pole gram volume of battery have significantly Lifting.The different section discharge curves of battery prepared by embodiment 6 are shown in Fig. 1.Cobalt acid lithium material wherein used in comparative example 1 is not Modified processing, positive pole gram volume lifting amplitude is maximum after it charges to 4.35V, corresponds to more lithium ions from stratiform cobalt acid lithium Structure in deviate from, for material in long-term circulation, the hidden danger degree of structure collapses is maximum.Cobalt used in embodiment 6 and comparative example 2 Sour lithium material passes through modification, and positive pole gram volume lifting amplitude is relatively small after it charges to 4.35V, the cobalt acid of modification Lithium may be limited to more lithium ions under 4.35V and deviate from from the structure of stratiform cobalt acid lithium, and the Stability Analysis of Structures of material is played Key effect.
In the 4.35V~3.0V high voltage region, the battery of embodiment 6 and comparative example 2 is carried out 7C, 10C, 25C, 35C and 45C multiplying power dischargings are tested, and test result is shown in Table 2.
The battery high rate performance contrast table that 2 different positive electrode active materials of table make
As known from Table 2, the multiplying power discharging ability of the battery of embodiment 6 is significantly better than comparative example 2.This is due to use Li2MnO3To LiCoO2Cladding processing is carried out, although LiCoO can be improved2High voltage stability, but clad is relatively weak Conductive capability reduces the large current discharging capability of material, and cobalt acid lithium is modified used by embodiment 6, possesses abundant ratio table Area and microcellular structure, the intercalation/deintercalation of lithium ion is especially advantageous for, greatly improves the multiplying power discharging ability of battery.
The battery of embodiment 6, comparative example 1 and comparative example 3 is subjected to circulation test using identical circulation system.Follow Ring system is：
Test temperature：25±3℃；
Charging modes：Use 7.5A (equivalent to 3C) constant-current constant-voltage chargings to 4.35V, cut-off current 0.03CmA；
Discharge mode：Use 50A (equivalent to 20C) constant-current discharges to 3.0V；
Cycle-index：Repeat above-mentioned circulation system 400 weeks.
Circulation the results are shown in Table 3.Circulation curve is shown in Fig. 2.
The battery circulation contrast table that 3 different positive electrode active materials of table make
As known from Table 3, the circulation ability of the battery of embodiment 6 is better than comparative example 1 and comparative example 3.This is due to reality Cobalt acid lithium is modified used by applying example 6, possesses more stable structure under 4.35V high voltage, it is longer to ensure that battery possesses Service life.Simultaneously because with the addition of ion liquid addictive in the electrolyte of embodiment 6, contribute to battery system in high electricity It is steady in a long-term under the conditions of pressure.
The battery of embodiment 6 and comparative example 3 is subjected to charged holding test using identical storing mode.Storing mode For：
Tester：Thermostatic drying chamber；
Test temperature：60±3℃；
Shelve the time：7 days.
Battery charge state：1C constant-current constant-voltage chargings are to 4.35V, cut-off current 0.03CmA；
Test result is shown in Table 4.
The battery charge storge quality contrast table of the different electrolytes of table 4
Group Conservation rate/% Recovery rate/% Internal resistance rate of change/% Thickness change/%
Embodiment 6 93.1 96.9 1.8 1.6
Comparative example 3 89.3 92.6 4.1 4.3
As known from Table 4, the charged storge quality of the battery of embodiment 6 is better than comparative example 3.This is due to the electrolysis of embodiment 6 Ion liquid addictive is with the addition of in liquid, contributes to battery system steady in a long-term under high voltage condition.
Embodiment 7
The present embodiment is same as Example 6, and wherein difference is：Lithium salt is 1.0mol/L in electrolyte, from Sub- liquid additive is N- methyl-N- acetoxyl groups-bis- (trifyl) imines piperidines ([MMEPip] [TFSI]), 1- second Base -3- methyl-bis- (fluorosulfonyl) imine imidazoles ([C2Mim] [FSA]) and N, N '-(fluoroform of diethyl -3- methylpyrazoles two Base sulphonyl) imines (DEMPyr123), mass concentration is respectively 1.0%, 1.0% and 1.0%.
Embodiment 8
The present embodiment is same as Example 6, and wherein difference is：Positive active material is D prepared by embodiment 250 Particle diameter is 6.0 μm and specific surface area is 0.85m2/ g modification cobalt acid lithium；Lithium salt is 1.2mol/L in electrolyte, ionic liquid Body additives are difluoro (oxalic acid) lithium borate (LiODFB), N- methyl-N- acetoxyl groups-bis- (trifyls) imines piperidines ([MMEPip] [TFSI]), 1- ethyl -3- methyl-bis- (fluorosulfonyl) imine imidazoles ([C2Mim] [FSA]) and N, N '-diethyl Base -3- methylpyrazoles two (trimethyl fluoride sulfonyl) imines (DEMPyr123), mass concentration are respectively 0.5%, 1.0%, 0.5% With 1.0%.
Embodiment 9
The present embodiment is same as Example 6, and wherein difference is：Positive active material is D prepared by embodiment 350 Particle diameter is 6.5 μm and specific surface area is 0.59m2/ g modification cobalt acid lithium；Lithium salt is 1.0mol/L in electrolyte, ionic liquid Body additives are N, N '-diethyl -3- methylpyrazoles two (trimethyl fluoride sulfonyl) imines (DEMPyr123), and mass concentration is 1.0%, the two-sided deposited charge level density of positive plate is 100g/m2, compacted density 3.4g/m3, the two-sided deposited charge level density of negative plate For 60g/m2, compacted density 1.3g/m3。
Embodiment 10
The present embodiment is same as Example 6, and wherein difference is：Positive active material is D prepared by embodiment 450 Particle diameter is 12.0 μm and specific surface area is 0.5m2/ g modification cobalt acid lithium；Lithium salt is 1.0mol/L in electrolyte, ionic liquid Body additives are N- methyl-N- acetoxyl groups-bis- (trifyl) imines piperidines ([MMEPip] [TFSI]), mass concentration For 1.0%.
Embodiment 11
The present embodiment is same as Example 6, and wherein difference is：Positive active material is D prepared by embodiment 250 Particle diameter is 8.5 μm and specific surface area is 0.68m2/ g modification cobalt acid lithium；Lithium salt is 1.2mol/L in electrolyte, ionic liquid Body additives are 1- ethyl -3- methyl-bis- (fluorosulfonyl) imine imidazoles ([C2Mim] [FSA]), mass concentration 0.5%, just The two-sided deposited charge level density of pole piece is 300g/m2, compacted density 3.9g/m3, the two-sided deposited charge level density of negative plate is 180g/ m2, compacted density 1.6g/m3。
In 4.35V~3.0V high voltage region, the survey of 25C and 45C multiplying power dischargings is carried out to the battery of embodiment 6 to 11 Examination, test result are shown in Table 5.
The embodiment 6 of table 5 to the battery of embodiment 11 multiplying power discharging test comparison table
In 4.35V~3.0V high voltage region, circulation test, test are carried out to the battery of embodiment 6 to 11 It the results are shown in Table 6.
Test temperature：25±3℃；
Charging modes：Use 7.5A (equivalent to 3C) constant-current constant-voltage chargings to 4.35V, cut-off current 0.03CmA；
Discharge mode：Use 50A (equivalent to 20C) constant-current discharges to 3.0V；
Cycle-index：Repeat above-mentioned circulation system 200 weeks.
The embodiment 6 of table 6 to the battery of embodiment 11 circulation contrast table
Group Capability retention (%) after 200 weeks
Embodiment 6 93.3
Embodiment 7 94.0
Embodiment 8 94.6
Embodiment 9 92.1
Embodiment 10 90.6
Embodiment 11 88.5
In summary, high voltage high multiplying power lithium ion battery of the invention, by using modified cobalt acid lithium, not only effectively carry High Stability Analysis of Structures of the stratiform cobalt acid lithium material under high-voltage state, and possess large current discharging capability.In the electrolytic solution Ionic liquid is added, improves battery long-term circulation under high voltages and storage capacity.Auxiliary ceramic membrane technique, afflux simultaneously Body technique and lug technology, it is 4.35V to realize a kind of charge cutoff voltage, and can carry out long-term 3C~45C circulations New type lithium ion battery.
It is described above, only it is presently preferred embodiments of the present invention, any restrictions is not done to the present invention, it is every according to invention skill Any simple modification, change and the equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention In the protection domain of scheme.

Claims (6)

1. a kind of high voltage high multiplying power lithium ion battery, including positive plate, negative plate, barrier film, electrolyte, positive pole ear, negative pole Lug and pack case, the positive plate are that the anode sizing agent containing positive active material is coated on into aluminium foil two sides and is made, and it is special Sign is that the charge cutoff voltage of the high voltage high multiplying power lithium ion battery is 4.35V, can support 3C~45C current discharges； The positive active material is D50Particle diameter is 4.0 μm~12.0 μm, specific surface area 0.5m2/ g~1.2m2/ g modified cobalt acid Lithium；
The preparation method of the modified cobalt acid lithium comprises the following steps：
Step 1: it is 0.5mol/ that cobalt chloride and metallic element M sulfate are configured into metal ion total concentration with deionized water L~1.5mol/L mixed solution, the pH value of the mixed solution is then adjusted with sodium hydroxide solution to 9~12, stirs 2h Centrifuge, precipitated after~6h；The precipitation is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing into Property, being deposited at 70 DEG C~90 DEG C after deionized water supersound washing is dried into 6h~12h, obtains metal ion mixing forerunner Body MyCo1-y(OH)2, wherein y=0.0001~0.1, the one or more in M Al, Cr, Ni and Mn；Again by the metal from Son doping presoma MyCo1-y(OH)2With lithium carbonate according to Li:Co=(1.05~1.1)：1 mixed in molar ratio, 500 DEG C~ 5h~10h is calcined under conditions of 1000 DEG C, obtains metal ion mixing cobalt acid lithium Li (MyCo1-y)O2；
Step 2: by metal ion mixing cobalt acid lithium Li (M described in organic carbon source and step 1yCo1-y)O2According to Li:C=1: It is placed in after the mixed in molar ratio of (3~5) in ptfe autoclave, using deionized water as reaction medium, 160 DEG C~220 24h~48h is reacted at DEG C, reacted material is first used into absolute ethyl alcohol supersound washing, then with deionized water supersound washing extremely Neutrality, the material after deionized water supersound washing is dried into 6h~12h at 70 DEG C~90 DEG C, obtains carbon coating cobalt acid lithium； The organic carbon source is the one or more in urea, grape sugar and starch；
Step 3: using absolute ethyl alcohol as decentralized medium, by external coating oxide, surfactant, filler and step 2 The carbon coating cobalt acid lithium is uniformly dispersed to obtain mixture, and then the mixture is heated at 60 DEG C~80 DEG C and is concentrated to give Gel, by the gel at 60 DEG C~200 DEG C heat resolve 1h~4h, then at 500 DEG C~1000 DEG C calcine 4h~9h, will Sieved after gel abrasive after calcining, obtain being modified cobalt acid lithium；The quality of the carbon coating cobalt acid lithium account for external coating oxide, The 65%~88.5% of surfactant, filler and carbon coating cobalt acid lithium gross mass, the quality of external coating oxide account for outer Clad oxide, surfactant, the 10%~30% of filler and carbon coating cobalt acid lithium gross mass, the matter of surfactant Amount accounts for the 1%~10% of external coating oxide, surfactant, filler and carbon coating cobalt acid lithium gross mass, filler Quality accounts for the 0.5%~5% of external coating oxide, surfactant, filler and carbon coating cobalt acid lithium gross mass；It is described outer Clad oxide is SiO2、ZrO2And CeO2In one or more, surfactant is sapn and/or tween, and filler is Polyurethanes.
A kind of 2. high voltage high multiplying power lithium ion battery according to claim 1, it is characterised in that y described in step 1 =0.05~0.1.
3. a kind of high voltage high multiplying power lithium ion battery according to claim 1, it is characterised in that contain in the electrolyte There is ion liquid addictive, the ion liquid addictive is difluoro (oxalic acid) lithium borate, N- methyl-N- acetoxyl groups-bis- (three Fluorine mesyl) imines piperidines, 1- ethyl -3- methyl-bis- (fluorosulfonyl) imine imidazoles and N, N '-diethyl -3- methyl pyrroles One or more in azoles two (trimethyl fluoride sulfonyl) imines.
A kind of 4. high voltage high multiplying power lithium ion battery according to claim 3, it is characterised in that in the electrolyte from The weight/mass percentage composition of sub- liquid additive is 0.5%~3.0%.
A kind of 5. high voltage high multiplying power lithium ion battery according to claim 1, it is characterised in that the negative plate be by Cathode size containing negative electrode active material is coated on copper foil two sides and is made, and the two-sided deposited charge level density of negative plate is 60g/m2~ 180g/m2, compacted density 1.3g/m3~1.6g/m3。
A kind of 6. high voltage high multiplying power lithium ion battery according to claim 1, it is characterised in that pair of the positive plate Dressing surface density in face is 100g/m2~300g/m2, compacted density 3.4g/m3~3.9g/m3。
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