CN102694201A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN102694201A CN102694201A CN2012101803291A CN201210180329A CN102694201A CN 102694201 A CN102694201 A CN 102694201A CN 2012101803291 A CN2012101803291 A CN 2012101803291A CN 201210180329 A CN201210180329 A CN 201210180329A CN 102694201 A CN102694201 A CN 102694201A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein each of the positive and plates consists of an active material, a conductive additive, an adhesive and a current collector; and the conductive additive is a three-dimensional space conductive network formed by mixing a zero-dimensional material, a one-dimensional material and a two-dimensional material. A specific cathode active material and a conductive carbon material with the three-dimensional space conductive network are adopted, and a small amount of wetting agent, a small amount of lithium salt stabilizing agent, a small amount of cathode film forming additive and a small amount of anode film forming protective agent are added into the electrolyte, so that the lithium ion battery can work under high cut-off voltage, and has the advantages of high cycling performance, high rate capability, high low-temperature performance, low high-temperature bulging and the like, and the energy density of the lithium ion battery is remarkably improved.
Description
Technical field
the invention belongs to technical field of lithium ion, are specifically related to a kind of lithium ion battery of high-energy-density.
Background technology
lithium ion battery becomes one of secondary cell of the widest model of application owing to have advantages such as energy density height, good cycle, operating voltage height, memory-less effect.Along with the develop rapidly of electronic technology, people have proposed higher energy density and longer requirements such as cycle performance to lithium ion battery.Therefore, develop high performance positive electrode and seem particularly important for the development of lithium ion battery.
In present commercial anode material for lithium-ion batteries, application the most extensively, the positive electrode of maturation is cobalt acid lithium (LiCoO the most
2
), its reversible gram volume under 4.2V work cut-ff voltage is merely about 140mAh/g, and is relatively low.Improve the operating voltage of battery, can make positive electrode give play to higher capacity, thereby improve the energy density of battery, as with LiCoO
2
Operating voltage bring up to 4.3V from present 4.2V, gram volume can improve 10%, and energy density can improve 5%.But along with the raising of operating voltage, electrolyte more is prone to the risk oxidized, that loop attenuation is quickened, security performance reduces, reality is used to be increased.
Recently, nickel cobalt manganese is ternary material Li (Ni
x
Co
y
Mn
1-x-y
) O
2
(0.3≤x≤0.8,0.1≤y≤0.4) is developed rapidly, and its cost is lower, and security performance is good, and in the capacity performance, has surpassed LiCoO
2
, more and more attract researcher's concern.
are that ternary material mixes use with lithium cobaltate cathode material with nickel cobalt manganese, can combine both advantages, to reach the reduction material cost, improve the chemical property of battery and the purpose of security performance.In addition, change LiCoO
2
Pattern, make it have the second particle pattern similar with ternary material, also can greatly improve its performance.In addition; Through certain means with a small amount of element-specific or its oxide mix equably get into the positive electrode body mutually in or be deposited on the positive electrode surface; Can effectively improve the side reaction of material surface and electrolyte; Thereby improve the high-temperature storage performance and the security performance of lithium ion battery, make material can be applied to higher charging cut-ff voltage following time and also have stable structure, thereby significantly promote battery capacity.
Summary of the invention
the objective of the invention is to, and a kind of lithium ion battery that is applicable to high charge cut-ff voltage condition and has high-energy-density is provided.
technical scheme of the present invention does; A kind of lithium ion battery; Comprise anode pole piece, cathode pole piece, barrier film and electrolyte; Anode pole piece and cathode pole piece are formed by active material, conductive additive, binding agent and collector, the three dimensions conductive network of conductive additive for being become by zero dimension, the mixing of peacekeeping two dimension material with carbon element.The conductive carbon material of sheet can form the conductive network framework; The conductive carbon of wire then can be interted between two-dimensional sheet conductive carbon aspect; Perhaps two-dimensional sheet conductive carbon outside forms the crosslinked conductive network of wire, and further, the zero dimension conductive carbon particle can be built into conductiving point between one dimension wire and two-dimensional sheet conductive carbon; Compensation is suspended on the electric conductivity of the small positive electrode particle in the perhaps planar network of wire; Thereby form effective three dimensions conductive network, the very big electric conductivity that improves the positive and negative electrode pole piece of degree significantly improves the high rate performance and the cryogenic property of battery.
As further improvement of the present invention, active material is made up of A, B, and wherein A is a primary particle, and B is for to assemble formed second particle by primary particle, and A is LiCoO
2
, B is LiCoO
2
A and B all mix to coat handle through element M, and doped chemical M is any one or two kinds among Mg, Ti, Al, Zr, the F; Coating is the oxide of any one or two kinds of elements among element M g, Ti, Al, the Zr etc., or phosphate, or fluoride, or the mixture of oxide, phosphate and fluoride.Wherein, the shared mass percent of A is 40 %-90%, and preferred scope is 60%-90%.Through effective means with a small amount of element-specific mix equably get into the positive electrode body mutually in; Or with its oxide or phosphate or fluoride uniform deposition on the positive electrode surface; Can effectively improve the side reaction of material surface and electrolyte; Thereby improve the high-temperature storage performance and the security performance of lithium ion battery, make material can be applied to higher charging cut-ff voltage following time and also have stable structure, thereby significantly promote battery capacity.
As further improvement of the present invention, active material is made up of A, B, and wherein A is a primary particle, and B is for to assemble formed second particle by primary particle, and A is LiCoO
2
, B is Li (Ni
x
Co
y
Mn
1-x-y
) O
2
, 0.3≤x≤0.8,0.1≤y≤0.4,0.6≤x+y≤0.9 wherein.A and B all mix to coat handle through element M, and doped chemical M is any one or two kinds among Mg, Ti, Al, Zr, the F; Coating is the oxide of any one or two kinds of elements among element M g, Ti, Al, the Zr etc., or phosphate, or fluoride, or the mixture of oxide, phosphate and fluoride.Wherein, the shared mass percent of A is 40 %-90%, and preferred scope is 60%-90%.LiCoO
2
The chemical property of material is comparatively stable, good cycle, but its structure is prone to destroy the thermal stability variation under the 4.2V charging cut-ff voltage being higher than.Nickel cobalt manganese is ternary material Li (Ni
x
Co
y
Mn
1-x-y
) O
2
Cost is lower, and security performance is good, and actual capacity can be up to 180-190 mAh/g, but its high temperature down and the electrolyte compatibility relatively poor.With nickel cobalt manganese is that ternary material mixes use with lithium cobaltate cathode material, can combine both advantages, with chemical property and the security performance of improving battery.In addition, change LiCoO
2
Pattern, make it have the second particle pattern similar with ternary material, with significantly improving lithium ion reversible dynamic behavior that takes off embedding in positive electrode, and reduce LiCoO
2
The possibility that structure is caved in significantly improves the cyclical stability of material under high cut-ff voltage condition.
Wetting agent, lithium salts stabilizer, anode film for additive and cathode filming protective agent are contained as further improvement of the present invention in
in the electrolyte.Wherein, wetting agent is cyclohexane or methyl last of the ten Heavenly stems, and the lithium salts stabilizer is LiPF 6 Or LiBF 4 , the cathode filming protective agent is BP (biphenyl).Use wetting agent can improve that electrolyte aligns under the electrolyte wettability in the positive and negative electrode pole piece, the especially low temperature, the infiltration of cathode pole piece; Use the anode film for additive; With the cathode filming protective agent; Can form excellent SEI (solid electrolyte) film or other passivating films on the battery active material surface; Thereby improve battery active material and electrolyte interface, suppress the side reaction of electrolyte, significantly improve the cycle performance of battery under high voltage; And add the lithium in small amounts salt stabilizing agent, can suppress the decomposition aerogenesis of electrolyte lithium salts, thereby improve cycle performance of battery, and guarantee that battery has lower high temperature bulging.
as further improvement of the present invention, the zero dimension material with carbon element is that particle is the conductive carbon black (SP) of 50-200nm, or acetylene black, or the graphite agent; The one dimension material with carbon element is carbon nano-fiber (VGCF) or CNT (CNT); The two dimension material with carbon element is a Graphene.And the percentage by weight that the zero dimension particle accounts for whole conductive additives is 10%-40%; The percentage by weight that the one dimension material with carbon element accounts for whole conductive additives is 10%-50%; The percentage by weight that the two dimension material with carbon element accounts for whole conductive additives is 20%-60%.
As further improvement of the present invention, Li (Ni
x
Co
y
Mn
1-x-y
) O
2
Be Li (Ni
0.8
Co
0.1
Mn
0.1
) O
2
, or Li (Ni
0.6
Co
0.2
Mn
0.2
) O
2
, or Li (Ni
0.5
Co
0.2
Mn
0.3
) O
2
, or Li (Ni
1/3
Co
1/3
Mn
1/3
) O
2
as further improvement of the present invention, the particle diameter D50 of A is 16-22 um.D50 is that the cumulative particle sizes percentile of a sample reaches 50% o'clock pairing particle diameter.To be particle diameter account for 50% greater than its particle to its physical significance, also accounts for 50% less than its particle, and D50 also is meso-position radius or median particle diameter.D50 is commonly used to represent the particle mean size of powder.
as further improvement of the present invention, the primary particle particle diameter D50 of B is 0.5-3.0 um, and second particle particle diameter D50 is 10-16um.
as further improvement of the present invention, and the anode film for additive is one or more the mixture among FEC (perfluorocarbon acid vinyl acetate), VA (vinyl acetate), VEC (vinylethylene carbonate), VC (vinylene carbonate), ES (ethylene sulfite), AN (acrylonitrile) and the SN (succinonitrile).
as further improvement of the present invention, work charging cut-ff voltage is 4.3V-4.5 V.
beneficial effect of the present invention is; Through constructing a kind of anode pole piece, cathode pole piece, barrier film and electrolyte of comprising; And conductive additive is for being mixed the lithium ion battery of the three dimensions conductive network that is become by zero dimension, peacekeeping two dimension material with carbon element; The zero dimension conductive carbon particle can be built into conductiving point between one dimension wire and two-dimensional sheet conductive carbon, compensation is suspended on the electric conductivity of the small positive electrode particle in the perhaps planar network of wire, thereby forms effective three dimensions conductive network; The very big electric conductivity that improves the positive and negative electrode pole piece of degree significantly improves the high rate performance and the cryogenic property of battery.
Description of drawings
Fig. 1 be the embodiment of the invention 1 with comparative example 1 in battery at the loop test curve of 3.0-4.35V.
Fig. 2 be the embodiment of the invention 1 with comparative example 1 in the ratio rate curve (4.35V-3.0V, 0.5C discharge) of the discharge capacity of battery under-20 ℃ and 25 ℃ of normal temperature discharge capacities.
Fig. 3 be the embodiment of the invention 1 with comparative example 1 in battery at the discharge-rate curve of 4.35-3.0V.
Embodiment
embodiment 1: a kind of lithium ion battery; Comprise anode pole piece, cathode pole piece, barrier film and electrolyte; Anode pole piece and cathode pole piece are formed by active material, conductive additive, binding agent and collector, the three dimensions conductive network of conductive additive for being become by zero dimension, the mixing of peacekeeping two dimension material with carbon element.The conductive carbon material of sheet can form the conductive network framework; The conductive carbon of wire then can be interted between two-dimensional sheet conductive carbon aspect; Perhaps two-dimensional sheet conductive carbon outside forms the crosslinked conductive network of wire, and further, the zero dimension conductive carbon particle can be built into conductiving point between one dimension wire and two-dimensional sheet conductive carbon; Compensation is suspended on the electric conductivity of the small positive electrode particle in the perhaps planar network of wire; Thereby form effective three dimensions conductive network, the very big electric conductivity that improves the positive and negative electrode pole piece of degree significantly improves the high rate performance and the cryogenic property of battery.
Active material is made up of A, B, and wherein A is a primary particle, and B is for to assemble formed second particle by primary particle, and A is LiCoO
2
, B is LiCoO
2
A and B all mix to coat handle through element M, and doped chemical M is any one or two kinds among Mg, Ti, Al, Zr, the F; Coating is the oxide of any one or two kinds of elements among element M g, Ti, Al, the Zr etc., or phosphate, or fluoride, or the mixture of oxide, phosphate and fluoride.Wherein, the shared mass percent of A is 40 %-90%, and preferred scope is 60%-90%.Through effective means with a small amount of element-specific mix equably get into the positive electrode body mutually in; Or with its oxide or phosphate or fluoride uniform deposition on the positive electrode surface; Can effectively improve the side reaction of material surface and electrolyte; Thereby improve the high-temperature storage performance and the security performance of lithium ion battery, make material can be applied to higher charging cut-ff voltage following time and also have stable structure, thereby significantly promote battery capacity.
Active material is made up of A, B, and wherein A is a primary particle, and B is for to assemble formed second particle by primary particle, and A is LiCoO
2
, B is Li (Ni
x
Co
y
Mn
1-x-y
) O
2
, 0.3≤x≤0.8,0.1≤y≤0.4,0.6≤x+y≤0.9 wherein.A and B all mix to coat handle through element M, and doped chemical M is any one or two kinds among Mg, Ti, Al, Zr, the F; Coating is the oxide of any one or two kinds of elements among element M g, Ti, Al, the Zr etc., or phosphate, or fluoride, or the mixture of oxide, phosphate and fluoride.Wherein, the shared mass percent of A is 40 %-90%, and preferred scope is 60%-90%.LiCoO
2
The chemical property of material is comparatively stable, good cycle, but its structure is prone to destroy the thermal stability variation under the 4.2V charging cut-ff voltage being higher than.Nickel cobalt manganese is ternary material Li (Ni
x
Co
y
Mn
1-x-y
) O
2
Cost is lower, and security performance is good, and actual capacity can be up to 180-190 mAh/g, but its high temperature down and the electrolyte compatibility relatively poor.With nickel cobalt manganese is that ternary material mixes use with lithium cobaltate cathode material, can combine both advantages, with chemical property and the security performance of improving battery.In addition, change LiCoO
2
Pattern, make it have the second particle pattern similar with ternary material, with significantly improving lithium ion reversible dynamic behavior that takes off embedding in positive electrode, and reduce LiCoO
2
The possibility that structure is caved in significantly improves the cyclical stability of material under high cut-ff voltage condition.
Contain wetting agent, lithium salts stabilizer, anode film for additive and cathode filming protective agent in
electrolyte.Wherein, wetting agent is cyclohexane or methyl last of the ten Heavenly stems, and the lithium salts stabilizer is LiPF 6 Or LiBF 4 , the cathode filming protective agent is BP (biphenyl).Use wetting agent can improve that electrolyte aligns under the electrolyte wettability in the positive and negative electrode pole piece, the especially low temperature, the infiltration of cathode pole piece; Use the anode film for additive; With the cathode filming protective agent; Can form excellent SEI (solid electrolyte) film or other passivating films on the battery active material surface; Thereby improve battery active material and electrolyte interface, suppress the side reaction of electrolyte, significantly improve the cycle performance of battery under high voltage; And add the lithium in small amounts salt stabilizing agent, can suppress the decomposition aerogenesis of electrolyte lithium salts, thereby improve cycle performance of battery, and guarantee that battery has lower high temperature bulging.
zero dimension material with carbon element is that particle is the conductive carbon black (SP) of 50-200nm, or acetylene black, or the graphite agent; The one dimension material with carbon element is carbon nano-fiber (VGCF) or CNT (CNT); The two dimension material with carbon element is a Graphene.And the percentage by weight that the zero dimension particle accounts for whole conductive additives is 10%-40%; The percentage by weight that the one dimension material with carbon element accounts for whole conductive additives is 10%-50%; The percentage by weight that the two dimension material with carbon element accounts for whole conductive additives is 20%-60%.
Xy1-x-y2
Be Li (Ni
0.8
Co
0.1
Mn
0.1
) O
2
, or Li (Ni
0.6
Co
0.2
Mn
0.2
) O
2
, or Li (Ni
0.5
Co
0.2
Mn
0.3
) O
2
, or Li (Ni
1/3
Co
1/3
Mn
1/3
) O
2
The particle diameter D50 of A is 16-22 um.D50 is that the cumulative particle sizes percentile of a sample reaches 50% o'clock pairing particle diameter.To be particle diameter account for 50% greater than its particle to its physical significance, also accounts for 50% less than its particle, and D50 also is meso-position radius or median particle diameter.D50 is commonly used to represent the particle mean size of powder.
The primary particle particle diameter D50 of
is 0.5-3.0 um, and second particle particle diameter D50 is 10-16um.
anode film for additive is one or more the mixture among FEC (perfluorocarbon acid vinyl acetate), VA (vinyl acetate), VEC (vinylethylene carbonate), VC (vinylene carbonate), ES (ethylene sulfite), AN (acrylonitrile) and the SN (succinonitrile).
work charging cut-ff voltage is 4.3V-4.5 V.
, further specify in the face of the present invention down below in conjunction with specific embodiment for further understanding characteristic of the present invention, technological means and the specific purposes that arrived, function.
anodal NMP (N-methyl pyrrolidone) that adopt are as solvent, and by active material: it is that 70% slurry evenly is coated on the Al paper tinsel that conductive carbon: PVDF (Kynoar)=95:2:3 is mixed with solid content.
negative pole adopts deionized water as solvent, and by graphite: it is that 45% slurry is evenly on the Cu paper tinsel that conductive carbon: SBR (butadiene-styrene rubber): CMC (sodium carboxymethylcellulose)=94:2:2:2 is mixed with solid content.
electrolyte is the LiPF6 solution of 1mol/L, and solvent is BP (biphenyl).
Positive pole, negative pole and barrier film that
will process are wound into electric core, through going into shell, closedtop, fluid injection, change into, operations such as moulding, detection process the finished product flexible-packed battery.Charge and discharge cycles test multiplying power is 0.5C/0.5C, and probe temperature is 45 ℃, and the charging cut-ff voltage is 4.2V-4.4V, and discharge cut-off voltage is 3.0V.
The used conductive additive of
present embodiment is mixed with the Graphene three by conductive carbon black (SP), carbon nano-fiber (VGCF), and wherein the SP particle is 50-200nm, and the percentage by weight of shared conductive additive is 20%; The length of VGCF is 500nm-6um, and the percentage by weight of shared conductive additive is 30%; Graphene adopts multi-layer graphene, and the percentage by weight of shared conductive additive is 50%.
Employed positive active material in the present embodiment is by the A with different-shape and two kinds of LiCoO of B
2
Form, wherein A is a primary particle, D50 is 18um; B is for to assemble formed second particle by primary particle, its grain diameter 1-2 um, and second particle particle diameter D50 is 14um; And the percentage by weight of the shared positive active material of A is 60%.
The dicyandiamide solution of the electrolyte that uses is EC:EMC:DEC in
present embodiment, and volume ratio is 1:1:1, and employed additive and addition thereof are: the about 0.2%-5% of FEC, the about 0.5%-2% of VEC, the about 0.1%-0.5% of BP, the about 1%-3% of SN.
present embodiment flexible-packed battery, the capability retention in the 3.0-4.35V voltage range after 1000 weeks of circulation is 83%, cyclic curve is as shown in Figure 1.The ratio of discharge capacity and the 25 ℃ normal temperature discharge capacities of battery under-20 ℃ is 58% (4.35V-3.0V, 0.5C discharge), and its curve is as shown in Figure 2.Battery is under 4.35-3.0V, and the ratio of 2C discharge capacity and 0.2C discharge capacity is 74%, and its discharge-rate curve is as shown in Figure 3.
embodiment 2: the used conductive additive of present embodiment is mixed by SP, CNT and Graphene three, and wherein the SP particle is 50-200nm, and the percentage by weight of shared conductive additive is 20%; The length of CNT is 500nm-5um, and the percentage by weight of shared conductive additive is 30%; Graphene adopts multi-layer graphene, and the percentage by weight of shared conductive additive is 50%.
Employed positive active material in the present embodiment is by the A with different-shape and two kinds of LiCoO of B
2
Form, wherein A is a primary particle, D50 is 18um; B is for to assemble formed second particle by primary particle, its grain diameter 1-2 um, and second particle particle diameter D50 is 14um; And the percentage by weight of the shared positive active material of A is 80%.
The dicyandiamide solution of the electrolyte that uses is EC:EMC:DEC in
present embodiment, and volume ratio is 1:1:1, and employed additive and addition thereof are: the about 0.2%-5% of VA, the about 0.5%-2% of VEC, the about 0.1%-0.5% of BP, the about 1%-3% of AN.
The flexible-packed battery of
present embodiment, the capability retention in the 3.0-4.35V voltage range after 1000 weeks of circulation is 80%.The ratio of discharge capacity and the 25 ℃ normal temperature discharge capacities of battery under-20 ℃ is 52% (4.35V-3.0V, 0.5C discharge).Battery is under 4.35-3.0V, and the ratio of 2C discharge capacity and 0.2C discharge capacity is 70%.
embodiment 3: the used conductive additive of present embodiment is mixed by SP, VGCF and Graphene three, and wherein the SP particle is 50-200nm, and the percentage by weight of shared conductive additive is 15%; The length of VGCF is 500nm-4um, and the percentage by weight of shared conductive additive is 25%; Graphene adopts multi-layer graphene, and the percentage by weight of shared conductive additive is 60%.
Employed positive active material in the present embodiment is by LiCoO
2
Primary particle and Li (Ni
0.5
Co
0.2
Mn
0.3
) O
2
Mix, wherein LiCoO
2
Particle diameter D50 is 19 merchant um; Li (Ni
0.5
Co
0.2
Mn
0.3
) O
2
The primary particle particle diameter be 1-2 um, second particle particle diameter D50 is 11um; And the percentage by weight of the shared positive active material of A is 60%.
The dicyandiamide solution of the electrolyte that uses is EC:EMC:DEC in
present embodiment, and volume ratio is 1:1:1, and employed additive and addition thereof are: the about 0.2%-5% of VC, the about 0.5%-2% of VEC, the about 0.1%-0.5% of BP, the about 1%-3% of AN.
The flexible-packed battery of
present embodiment, the capability retention in the 3.0-4.35V voltage range after 1000 weeks of circulation is 78%.The ratio of discharge capacity and the 25 ℃ normal temperature discharge capacities of battery under-20 ℃ is 46% (4.35V-3.0V, 0.5C discharge).Battery is under 4.35-3.0V, and the ratio of 2C discharge capacity and 0.2C discharge capacity is 68%.
embodiment 4: the used conductive additive of present embodiment is mixed by SP, CNT and Graphene three, and wherein the SP particle is 50-200nm, and the percentage by weight of shared conductive additive is 30%; The length of CNT is 500nm-5um, and the percentage by weight of shared conductive additive is 40%; Graphene adopts multi-layer graphene, and the percentage by weight of shared conductive additive is 40%.
Employed positive active material in the present embodiment is by LiCoO
2
Primary particle and Li (Ni
0.6
Co
0.2
Mn
0.2
) O
2
Mix, wherein LiCoO
2
Particle diameter D50 is 16 merchant um; Li (Ni
0.6
Co
0.2
Mn
0.2
) O
2
The primary particle particle diameter be 1-2 um, second particle particle diameter D50 is 10um; And the percentage by weight of the shared positive active material of A is 70%.
The dicyandiamide solution of the electrolyte that uses is EC:EMC:DEC in
present embodiment, and volume ratio is 1:1:1, and employed additive and addition thereof are: the about 0.2%-5% of VA, the about 0.5%-2% of VEC, the about 0.1%-0.5% of BP, the about 1%-3% of AN.
The flexible-packed battery of
present embodiment, the capability retention in the 3.0-4.35V voltage range after 1000 weeks of circulation is 76%.The ratio of discharge capacity and the 25 ℃ normal temperature discharge capacities of battery under-20 ℃ is 45% (4.35V-3.0V, 0.5C discharge).Battery is under 4.35-3.0V, and the ratio of 2C discharge capacity and 0.2C discharge capacity is 65%.
comparative example 1: the used conductive additive of present embodiment is SP, and its granularity is 50-200nm.
Employed positive active material in the present embodiment is by LiCoO
2
Primary particle is formed, and its particle diameter D50 is 18um.
The dicyandiamide solution of the electrolyte that uses is EC:EMC:DEC in
present embodiment, and volume ratio is 1:1:1.
The flexible-packed battery of
present embodiment, the capability retention in the 3.0-4.35V voltage range after 700 weeks of circulation is 70%, cyclic curve is as shown in Figure 1.The ratio of discharge capacity and the 25 ℃ normal temperature discharge capacities of battery under-20 ℃ is 15% (4.35V-3.0V, 0.5C discharge), and its curve is as shown in Figure 2.Battery is under 4.35-3.0V, and the ratio of 2C discharge capacity and 0.2C discharge capacity is 45%, and its discharge-rate curve is as shown in Figure 3.
above-mentioned embodiment is the preferred embodiments of the present invention; Can not limit claim of the present invention; Anyly utilize the change done under the disclosed technology contents, modification, substitute, combination, simplify, all should be equivalent embodiment, and do not break away from technical characterictic content of the present invention; All still belong to the scope of technical characterictic of the present invention, be included within protection scope of the present invention.
Claims (10)
1. lithium ion battery; Comprise anode pole piece, cathode pole piece, barrier film and electrolyte; It is characterized in that; Said anode pole piece and cathode pole piece comprise active material, conductive additive, binding agent and collector respectively, the three dimensions conductive network of said conductive additive for being become by zero dimension material with carbon element, one dimension material with carbon element and the mixing of two-dimentional material with carbon element.
2. according to the said lithium ion battery of claim 1, it is characterized in that said active material is made up of A, B, wherein A is a primary particle, and B is for to assemble formed second particle by primary particle, and said A is LiCoO
2, B is LiCoO
2
3. according to the said lithium ion battery of claim 1, it is characterized in that said active material is made up of A, B, wherein A is a primary particle, and B is for to assemble formed second particle by primary particle, and said A is LiCoO
2, B is Li (Ni
xCo
yMn
1-x-y) O
2, 0.3≤x≤0.8,0.1≤y≤0.4,0.6≤x+y≤0.9 wherein.
4. according to the said lithium ion battery of claim 1, it is characterized in that, contain wetting agent, lithium salts stabilizer, anode film for additive and cathode filming protective agent in the said electrolyte.
5. according to the said lithium ion battery of claim 1, it is characterized in that said zero dimension material with carbon element is that particle is the conductive carbon black (SP) of 50-200nm, or acetylene black, or the graphite agent; Said one dimension material with carbon element is carbon nano-fiber (VGCF) or CNT (CNT); Said two-dimentional material with carbon element is a Graphene.
6. according to the said lithium ion battery of claim 3, it is characterized in that said Li (Ni
xCo
yMn
1-x-y) O
2Be Li (Ni
0.8Co
0.1Mn
0.1) O
2, Li (Ni
0.6Co
0.2Mn
0.2) O
2, Li (Ni
0.5Co
0.2Mn
0.3) O
2Perhaps Li (Ni
1/3Co
1/3Mn
1/3) O
2In any one.
7. according to the said lithium ion battery of claim 2, it is characterized in that the particle diameter D50 of said A is 16-22 um.
8. according to the said lithium ion battery of claim 2, it is characterized in that the primary particle particle diameter D50 of said B is 0.5-3.0 um, second particle particle diameter D50 is 10-16um.
9. according to the said lithium ion battery of claim 4; It is characterized in that said anode film for additive is one or more the mixture among FEC (perfluorocarbon acid vinyl acetate), VA (vinyl acetate), VEC (vinylethylene carbonate), VC (vinylene carbonate), ES (ethylene sulfite), AN (acrylonitrile) and the SN (succinonitrile).
10. according to the said lithium ion battery of claim 1, it is characterized in that work charging cut-ff voltage is 4.3V-4.5 V.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101803291A CN102694201A (en) | 2012-06-04 | 2012-06-04 | Lithium ion battery |
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| CN104600265A (en) * | 2015-01-06 | 2015-05-06 | 中国科学院化学研究所 | High-performance carbon-sulfur composite anode material and preparation method thereof |
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| CN109494346A (en) * | 2018-10-25 | 2019-03-19 | 电子科技大学 | A kind of preparation method of carbon quantum dot modification lithium sulfur battery anode material |
| CN109786724A (en) * | 2019-03-11 | 2019-05-21 | 贵州省铜仁华迪斯新能源有限公司 | A kind of ultralow-temperature high-rate type lithium ion cell and preparation method thereof |
| CN109980199A (en) * | 2019-03-20 | 2019-07-05 | 宁德新能源科技有限公司 | Negative electrode active material and preparation method thereof and the device for using the negative electrode active material |
| CN109980199B (en) * | 2019-03-20 | 2020-09-29 | 宁德新能源科技有限公司 | Negative active material, method for preparing same, and device using same |
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