CN107623142A - A kind of high power lithium ion power battery - Google Patents
A kind of high power lithium ion power battery Download PDFInfo
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- CN107623142A CN107623142A CN201710819637.7A CN201710819637A CN107623142A CN 107623142 A CN107623142 A CN 107623142A CN 201710819637 A CN201710819637 A CN 201710819637A CN 107623142 A CN107623142 A CN 107623142A
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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
- 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
Abstract
The invention discloses a kind of high power lithium ion power battery, including anode pole piece, barrier film, cathode pole piece, electrolyte, external terminal and shell；Described anode pole piece is made by plus plate current-collecting body and coated on the positive active material on plus plate current-collecting body；The positive active material includes positive electrode, conductive agent and binding agent, and wherein positive electrode is the iron manganese phosphate lithium material with olivine structural, and the molecular formula of the iron manganese phosphate lithium material is LiMnxFe1‑ xPO4, wherein 0.2≤x≤0.8；The electrolyte is made up of electrolyte lithium salt, organic solvent and both positive and negative polarity film for additive.Cell positive material of the present invention uses iron manganese phosphate lithium material, improves battery energy density, improves power of battery characteristic, ensures the security feature of battery.Electrolyte uses electrolyte lithium salt, organic solvent and both positive and negative polarity film for additive, reduces pole piece internal resistance, prevents the dissolution of metal ion in high temperature positive pole, improves power of battery performance and high-temperature behavior.
Description
Technical field
The present invention relates to lithium ion power battery technology field, specifically a kind of high power lithium ion power battery.
Background technology
As people strengthen environmental protection consciousness, electric automobile progressively comes into current consumption market.Electric automobile in front
It is broadly divided into pure electric automobile and hybrid vehicle.For hybrid vehicle, market demands are keeping the feelings of the power of battery
Under condition, course continuation mileage and durability are improved, this just needs to improve battery energy density and high-temperature behavior.
Current Chinese hybrid vehicle market, cell positive material mainly use the LiFePO4 material of olivine structural
Material, the LiFePO4 (LiFePO of olivine structural4), there is the advantages of safe, but discharge voltage low (3.3V) be present, shake
The deficiencies such as real density is low.Japan and Korea S and European ＆ American Market, cell positive material mainly use the lithium manganate material of layer structure, but high
Warm poor-performing.Some uses nickel-cobalt-manganese ternary material as positive pole, material gram volume, compacted density and electricity in the prior art
Pond energy density is higher than LiFePO4 and LiMn2O4 system, but security is poor.
The content of the invention
It is an object of the invention to provide a kind of high power lithium ion power battery, to solve to propose in above-mentioned background technology
The problem of.
To achieve the above object, the present invention provides following technical scheme：
A kind of high power lithium ion power battery, including anode pole piece, barrier film, cathode pole piece, electrolyte, external terminal and
Shell；Described anode pole piece is made by plus plate current-collecting body and coated on the positive active material on plus plate current-collecting body；It is described
Positive active material includes positive electrode, conductive agent and binding agent, and wherein positive electrode is the manganese phosphate with olivine structural
Iron lithium material, the molecular formula of the iron manganese phosphate lithium material is LiMnxFe1-xPO4, wherein 0.2≤x≤0.8；The electrolyte by
Electrolyte lithium salt, organic solvent and both positive and negative polarity film for additive composition.
As the further scheme of the present invention：The molecular formula of the iron manganese phosphate lithium material is LiMnxFe1-xPO4, wherein
0.4≤x≤0.5。
As the further scheme of the present invention：The primary particle scope of the iron manganese phosphate lithium material is 20~500nm, carbon
1.0~5wt% of content, 10~40m of specific surface area2/g。
As the further scheme of the present invention：20~200nm of primary particle of the iron manganese phosphate lithium material, carbon content
1.8~3.0%, 20~35m of specific surface area2/g。
As the further scheme of the present invention：The chemical combination of the iron manganese phosphate lithium material cladding and/or 1~10wt% of doping
Thing, the compound are at least three in F, Ti, Al, Mg, V, Zn, F, Zr, Cr, Ru, Mo, Ni, Co, W and rare-earth compound
Kind.
As the further scheme of the present invention：The two-sided surface density of anode pole piece is 90~150g/m2, conductive agent contains
Measure as the 3~6% of positive active material quality.
As the further scheme of the present invention：The electrolyte lithium salt molar concentration is 0.8~1.5mol/L, wherein
LiTFSi molar content is the 1~30% of electrolyte lithium salt.
As the further scheme of the present invention：Contain nitrile compounds, nitrile chemical combination in the both positive and negative polarity film for additive
Thing is at least one of adiponitrile (AND) and succinonitrile (SN), and the content of nitrile compounds is both positive and negative polarity film for additive matter
The 0.5~5% of amount.
As the further scheme of the present invention：The content of nitrile compounds for both positive and negative polarity film for additive quality 0.5~
2%.
As the further scheme of the present invention：The both positive and negative polarity film for additive contains sulfur ester, thioesters class
Compound is at least one of propylene sulfite (PS) and ethylene sulfite (ES), and the content of sulfur ester is positive and negative
The 0.5~5% of pole film for additive quality.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) cell positive material uses iron manganese phosphate lithium material, and material has two voltage platforms of 4.1V and 3.4V, improves electricity
Pond energy density, improve power of battery characteristic.Simultaneously because the iron manganese phosphate for lithium material safety of olivine structural can be good, ensure
The security feature of battery.
(2) electrolyte uses electrolyte lithium salt, organic solvent and both positive and negative polarity film for additive, reduces pole piece internal resistance, prevents
The dissolution of metal ion in high temperature positive pole, improve power of battery performance and high-temperature behavior.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. are equal
It is commercially available or the industry is conventional.
The high power lithium ion power battery include anode pole piece, barrier film, cathode pole piece, electrolyte, external terminal and
Shell.Described anode pole piece is made by plus plate current-collecting body and coated on the positive active material on plus plate current-collecting body.It is described
Positive active material includes positive electrode, conductive agent and binding agent, and wherein positive electrode is the manganese phosphate with olivine structural
Iron lithium material.The electrolyte is made up of electrolyte lithium salt, organic solvent and both positive and negative polarity film for additive.
High-performance lithium ion electrokinetic cell, the battery include anode pole piece, barrier film, cathode pole piece, electrolyte, external connection end
Son, shell.
The anode pole piece makes：It is LiMn by molecular formulaxFe1-xPO4Olivine structural iron manganese phosphate lithium material, it is molten
Agent such as N-N- dimethyl pyrrolidones, conductive black such as SP or ECP, CNT (CNT or WCNT), flaky graphite, gas
A kind of material or different materials such as phase grown carbon fiber (VGCF), binding agent such as polyvinylidene fluoride (PVDF), according to certain
It is coated uniformly on after ratio mixing on aluminium foil, dries, roll, film-making.
The barrier film：Using the barrier film with microcellular structure such as PP, PE, PP-PE-PP, barrier film porosity is 40-
60%.
The cathode pole piece is by by negative material such as native graphite, Delanium, soft carbon, hard carbon, solvent such as N-
N- dimethyl pyrrolidones or deionized water, conductive black such as SP or ECP, CNT (CNT or WCNT), flaky graphite,
At least one materials such as gas-phase growth of carbon fibre (VGCF), binding agent such as polyvinylidene fluoride (PVDF), polyamide (PI), gather
Acrylic acid, sodium carboxymethylcellulose (CMC), fourth breast rubber (SBR), uniformly ground after mixing coated in being dried on negative current collector
Pressure, film-making.
The electrolyte main electrolyte lithium salts, both positive and negative polarity film for additive and include such as lithium hexafluoro phosphate, carbonic acid two
The mixture of the organic solvents such as methyl esters, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester composition, both positive and negative polarity
Film for additive includes the materials such as vinylene carbonate, propylene sulfite.
The external terminal, positive pole use aluminium material, and negative pole uses copper nickel plating material.
Affiliated shell is one kind in plastic housing, box hat, aluminum hull or aluminum plastic film.
Comparative example 1
Prepare anode pole piece：Mix the LiFePO4 of 92 parts by weight, the Ketjen black (ECP) of 2 parts by weight, the gas of 2 parts by weight
Phase grown carbon fiber (VGCF), and the Kynoar (PVDF) of 4 parts by weight, and add the stirring of N-N- dimethyl pyrrolidones
Slurries are formed, are coated uniformly on aluminium foil, two-sided surface density 110g/m2, rolled after drying with roller, positive pole pole be made
Piece.
Prepare cathode pole piece：Mix the Delanium of 94 parts by weight, the conductive black SP of 1.3 parts by weight, 0.7 parts by weight
Gas-phase growth of carbon fibre (VGCF), the sodium carboxymethylcellulose (CMC) of 1.5 parts by weight and the butadiene-styrene rubber of 2.5 parts by weight
(SBR), and add deionized water and stir to form slurries, uniformly coated on negative pole base flow body copper foil, roller is used after drying
Rolled, cathode pole piece is made.
Prepare barrier film：Barrier film uses thickness as 20 microns of polypropylene microporous composite membrane (PE), air permeability 207cm3/ sec,
Porosity 45%.
Prepare electrolyte：Electrolyte is dissolved into methyl ethyl carbonate, ethylene carbonate using 1.15mol/L lithium hexafluoro phosphate
In the ORGANIC SOLVENT MIXTURES of ester, vinylene carbonate and propylene sulfite, wherein methyl ethyl carbonate, ethylene carbonate, carbon
The volume ratio of sour vinylene and propylene sulfite is (68: 28.5: 2: 1.5).
Prepare shell：Shell uses aluminum plastic film.
Prepare external terminal：Positive terminal uses 0.3 millimeters thick aluminium material lug, and negative terminal is plated using 0.2 millimeter of copper
Nickel lug.
Prepare battery：With laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed into battery core, weld pole
Ear；Then aluminum plastic film heat-sealing is carried out, injects electrolyte, heat-sealing sealing；Carry out shelving-preliminary filling-evacuation-chemical conversion-partial volume successively
(3.6~2.0V), 10Ah lithium-ion-power cells are made.
Embodiment 1
Unlike comparative example 1：Positive pole uses LiMn0.48Fe0.52PO4, 20~200nm of primary particle, carbon content
2.35wt%, specific surface area 28m2/g。
Prepare electrolyte：Electrolyte is using 1.15mol/L lithium hexafluoro phosphate and 0.15mol/L double fluoroform sulphonyl
Imine lithium is dissolved into the ORGANIC SOLVENT MIXTURES of ethylene carbonate, propene carbonate and methyl ethyl carbonate, wherein ethylene carbonate
The volume ratio of ester, propene carbonate and methyl ethyl carbonate is 28: 7: 65, and it is sub- then to sequentially add the carbonic acid that quality accounting is 1%
Vinyl acetate, 1% propylene sulfite, 2% ethylene sulfite and 1.5% succinonitrile uniformly mix, and obtain electrolyte.
4.1~2.0V of battery charging and discharging blanking voltage.
The equivalent comparative example 1 of barrier film, cathode pole piece and both positive and negative polarity Capacity Ratio (N/P ratios).
Embodiment 2
Unlike comparative example 1：Positive pole uses LiMn0.45Fe0.55PO4, 20~200nm of primary particle, carbon content
2.08wt%, specific surface area 31m2/g。
Prepare electrolyte：Electrolyte is using 1.05mol/L lithium hexafluoro phosphate and 0.25mol/L double fluoroform sulphonyl
Imine lithium is dissolved into the ORGANIC SOLVENT MIXTURES of ethylene carbonate, propene carbonate and methyl ethyl carbonate, wherein ethylene carbonate
The volume ratio of ester, propene carbonate and methyl ethyl carbonate is 28: 7: 65, and it is sub- then to sequentially add the carbonic acid that quality accounting is 2%
Vinyl acetate, 1.3% propylene sulfite, 1% ethylene sulfite and 0.85% adiponitrile uniformly mix, and are electrolysed
Liquid.
4.1~2.0V of battery charging and discharging blanking voltage.
The equivalent comparative example 1 of barrier film, cathode pole piece and both positive and negative polarity Capacity Ratio (N/P ratios).
Embodiment 3
Unlike comparative example 1：Positive pole uses LiMn0.5Fe0.5PO4, 20~200nm of primary particle, carbon content
2.2wt%, specific surface area 30m2/g。
Prepare electrolyte：Electrolyte is sub- using 1.1mol/L lithium hexafluoro phosphate and 0.2mol/L double fluoroform sulphonyl
Amine lithium is dissolved into the ORGANIC SOLVENT MIXTURES of ethylene carbonate, propene carbonate and methyl ethyl carbonate, wherein ethylene carbonate,
The volume ratio of propene carbonate and methyl ethyl carbonate is 28: 7: 65, then sequentially adds the carbonic acid Asia second that quality accounting is 1.5%
Alkene ester, 0.8% propylene sulfite, 1.5% ethylene sulfite and 2% succinonitrile uniformly mix, and obtain electrolyte.
4.1~2.0V of battery charging and discharging blanking voltage.
The equivalent comparative example 1 of barrier film, cathode pole piece and both positive and negative polarity Capacity Ratio (N/P ratios).
Embodiment 4
Unlike comparative example 1：Positive pole uses LiMn0.4Fe0.6PO4, 20~200nm of primary particle, carbon content
2.0wt%, specific surface area 25m2/g。
Prepare electrolyte：Electrolyte is using 1.0mol/L lithium hexafluoro phosphate and 0.15mol/L double fluoroform sulphonyl
Imine lithium is dissolved into the ORGANIC SOLVENT MIXTURES of ethylene carbonate, propene carbonate and methyl ethyl carbonate, wherein ethylene carbonate
The volume ratio of ester, propene carbonate and methyl ethyl carbonate is 28: 7: 65, then sequentially adds the carbonic acid that quality accounting is 1.8%
Vinylene, 1.0% propylene sulfite, 1.8% ethylene sulfite and 1.8% succinonitrile uniformly mix, and obtain
Electrolyte.
4.1~2.0V of battery charging and discharging blanking voltage.
The equivalent comparative example 1 of barrier film, cathode pole piece and both positive and negative polarity Capacity Ratio (N/P ratios)
Embodiment 5
Unlike comparative example 1：Positive pole uses LiMn0.46Fe0.54PO4, 20~200nm of primary particle, carbon content
2.5wt%, specific surface area 20m2/g。
Prepare electrolyte：Electrolyte is sub- using 1.1mol/L lithium hexafluoro phosphate and 0.2mol/L double fluoroform sulphonyl
Amine lithium is dissolved into the ORGANIC SOLVENT MIXTURES of ethylene carbonate, propene carbonate and methyl ethyl carbonate, wherein ethylene carbonate,
The volume ratio of propene carbonate and methyl ethyl carbonate is 28: 7: 65, then sequentially adds the vinylene carbonate that quality accounting is 2%
Ester, 1.3% propylene sulfite, 1.5% ethylene sulfite and 0.8% adiponitrile uniformly mix, and obtain electrolyte.
4.1~2.0V of battery charging and discharging blanking voltage.
The equivalent comparative example 1 of barrier film, cathode pole piece and both positive and negative polarity Capacity Ratio (N/P ratios)
Energy density is tested：
Battery made from above-described embodiment and comparative example 1 is respectively taken into 3 measure, 23 DEG C of energy densities.Assay method is：
At 23 DEG C then electric current is turned into constant-voltage charge, by electric current 0.05C with 1C constant current charges to upper voltage limit；Shelve 10 points
Clock, assigned voltage is discharged to 20C constant currents, measure obtains the discharge capacity of battery；After shelving 15 minutes, above-mentioned step is repeated
Rapid 3 times, calculate 3 discharge capacity average values.Service precision is the weight of 0.1g electronic balance weighing different type battery.Press
23 DEG C of battery energy densities are calculated according to following formula：
Battery energy density=battery discharging energy/battery weight.
Battery energy density test result is shown in Table 1.As seen from the table, anode is made using iron manganese phosphate lithium material
Battery energy density is higher by 20% or so using the battery energy density of LiFePO4 than positive pole.
High temperature cyclic performance is tested：
Battery, with 1C constant current charges to upper voltage limit, then turns constant-voltage charge at 45 DEG C, by electric current 0.05C；
Shelve 10 minutes, lower voltage limit is discharged to 2C constant currents, measure obtains the initial discharge capacity C0 of battery；Shelve 10 minutes
Afterwards, repeat the above steps 1500 times, make continuous charge-discharge test, obtain the capacity C 1 after 1500 circulations of battery.Under
Formula calculates the capacity surplus ratio of battery after 1500 circulations：Capacity surplus ratio=C1/C0 × 100%.
As can be known from Table 1, anode uses iron manganese phosphate lithium material, electrolyte addition electrolyte lithium salt and both positive and negative polarity into
After film additive, battery is increased dramatically in high temperature circulation performance.
Table 1
| Detection project | Battery energy density (Wh/Kg) | Capacity surplus ratio (%) after 45 DEG C of -1500 circulations |
| Comparative example 1 | 90 | 75.0 |
| Embodiment 1 | 112 | 86.7 |
| Embodiment 2 | 108 | 87.3 |
| Embodiment 3 | 110 | 84.1 |
| Embodiment 4 | 107 | 88.3 |
| Embodiment 5 | 108 | 87.2 |
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (10)
1. a kind of high power lithium ion power battery, including anode pole piece, barrier film, cathode pole piece, electrolyte, external terminal and outer
Shell；Described anode pole piece is made by plus plate current-collecting body and coated on the positive active material on plus plate current-collecting body；Its feature
It is, the positive active material includes positive electrode, conductive agent and binding agent, and wherein positive electrode is with olivine structural
Iron manganese phosphate lithium material, the molecular formula of the iron manganese phosphate lithium material is LiMnxFe1-xPO4, wherein 0.2≤x≤0.8；It is described
Electrolyte is made up of electrolyte lithium salt, organic solvent and both positive and negative polarity film for additive.
2. high power lithium ion power battery according to claim 1, it is characterised in that the iron manganese phosphate lithium material
Molecular formula is LiMnxFe1-xPO4, wherein 0.4≤x≤0.5.
3. high power lithium ion power battery according to claim 1, it is characterised in that the iron manganese phosphate lithium material
Primary particle scope is 20~500nm, 1.0~5wt% of carbon content, 10~40m of specific surface area2/g。
4. high power lithium ion power battery according to claim 3, it is characterised in that the iron manganese phosphate lithium material
20~200nm of primary particle, carbon content 1.8~3.0%, 20~35m of specific surface area2/g。
5. high power lithium ion power battery according to claim 1, it is characterised in that the iron manganese phosphate lithium material bag
1~10wt% compound is covered and/or adulterates, the compound is F, Ti, Al, Mg, V, Zn, F, Zr, Cr, Ru, Mo, Ni, Co, W
With at least three kinds in rare-earth compound.
6. high power lithium ion power battery according to claim 1, it is characterised in that the two-sided face of anode pole piece is close
Spend for 90~150g/m2, the content of conductive agent is the 3~5% of positive active material quality.
7. high power lithium ion power battery according to claim 1, it is characterised in that the electrolyte lithium salt mole is dense
Spend for 0.8~1.5mol/L, wherein LiTFSi molar content is the 1~30% of electrolyte lithium salt.
8. high power lithium ion power battery according to claim 1, it is characterised in that the both positive and negative polarity film for additive
In contain nitrile compounds, nitrile compounds are at least one of adiponitrile and succinonitrile, and the content of nitrile compounds is just
The 0.5~5% of cathode film formation additive quality.
9. high power lithium ion power battery according to claim 1, it is characterised in that the content of nitrile compounds is just
The 0.5~2% of cathode film formation additive quality.
10. high power lithium ion power battery according to claim 1, it is characterised in that the both positive and negative polarity film forming addition
Agent contains sulfur ester, and sulfur ester is at least one of propylene sulfite and ethylene sulfite, and sulphur adds
Agent contains sulfur ester, and sulfur ester is at least one of propylene sulfite and ethylene sulfite, thioesters
The content of class compound is the 0.5~5% of both positive and negative polarity film for additive quality.
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| CN111710917A (en) * | 2020-06-22 | 2020-09-25 | 中国电力科学研究院有限公司 | Manganese lithium ion battery for direct-current power supply and preparation method thereof |
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| CN114597346A (en) * | 2020-12-02 | 2022-06-07 | 通用汽车环球科技运作有限责任公司 | Thick electrodes for electrochemical cells |
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| CN114094201A (en) * | 2022-01-24 | 2022-02-25 | 深圳市睿赛新能源科技有限公司 | Lithium iron phosphate battery |
| CN115275319A (en) * | 2022-06-17 | 2022-11-01 | 江苏正力新能电池技术有限公司 | Lithium ion battery and battery pack |
| CN115275319B (en) * | 2022-06-17 | 2024-02-13 | 江苏正力新能电池技术有限公司 | Lithium ion battery and battery pack |
| CN115425277A (en) * | 2022-08-26 | 2022-12-02 | 江苏正力新能电池技术有限公司 | Lithium ion battery |
| CN115548422A (en) * | 2022-10-17 | 2022-12-30 | 江苏正力新能电池技术有限公司 | Lithium ion battery |
| CN115579507A (en) * | 2022-10-21 | 2023-01-06 | 江苏正力新能电池技术有限公司 | Secondary battery and preparation method thereof, battery pack and power utilization device |
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