US 2017.0062869A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2017/0062869 A1 Zhamu et al. (43) Pub. Date: Mar. 2, 2017 (54) RECHARGEABLE LITHIUM BATTERIES (52) U.S. Cl. HAVING ANULTRA-HIGHVOLUMETRIC CPC ....... H0IM 10/0525 (2013.01); H0IM 4/131 ENERGY DENSITY AND REQUIRED (2013.01); H0IM 4/133 (2013.01); H0IM PRODUCTION PROCESS 4/134 (2013.01); H01 M 4/136 (2013.01); H0IM 4/137 (2013.01); H01 M 4/13 (71) Applicants: Aruna Zhamu, Springboro, OH (US); (2013.01); H0 IM 4/364 (2013.01); H0IM Bor Z. Jang, Centerville, OH (US) 4/386 (2013.01); H01 M 4/523 (2013.01); H0IM 4/483 (2013.01); H01 M 4/502 (72) Inventors: Aruna Zhamu, Springboro, OH (US); (2013.01); H01 M 4/60 (2013.01); H0IM Bor Z. Jang, Centerville, OH (US) 4/602 (2013.01); H01 M 4/581 (2013.01); H0IM 4/5815 (2013.01); H0IM 4/5825 (21) Appl. No.: 14/756,293 (2013.01); H01 M 4/5835 (2013.01); H0IM 4/587 (2013.01); H01 M 4/661 (2013.01); (22) Filed: Aug. 24, 2015 H01 M 4/663 (2013.01); H01 M 4/667 (2013.01); H0IM 4/808 (2013.01); H0IM Publication Classification 2/1653 (2013.01); H0IM 10/0585 (2013.01); (51) Int. Cl. HOIM 2004/021 (2013.01) HIM IO/0525 (2006.01) HOLM 4/33 (2006.01) HOLM 4/34 (2006.01) (57) ABSTRACT HOLM 4/36 (2006.01) HOLM 4/37 (2006.01) A process for producing a lithium battery, comprising: (A) HOLM 4/3 (2006.01) Assembling a porous cell framework composed of a foamed HOLM 4/36 (2006.01) anode current collector, a foamed cathode current collector, HOLM 4/38 (2006.01) and a porous separator disposed between the two collectors; HOLM 4/52 (2006.01) wherein the current collector(s) has a thickness no less than HOLM 4/48 (2006.01) 100 um and at least 80% by volume of pores; (B) Preparing HOLM 4/50 (2006.01) a first Suspension of an anode active material dispersed in a HOLM 4/60 (2006.01) first liquid electrolyte and a second Suspension of a cathode HOLM 4/58 (2006.01) active material dispersed in a second liquid electrolyte; and HOLM 4/583 (2006.01) (C) Injecting the first Suspension into pores of the anode HOLM 4/587 (2006.01) current collector to form an anode and injecting the second HOLM 4/66 (2006.01) Suspension into pores of the cathode current collector to HOLM 4/80 (2006.01) form a cathode to an extent that the anode active material HOLM 2/6 (2006.01) and the cathode active material combined constitutes an HIM IO/0585 (2006.01) electrode active material mass loading no less than 40% of HOLM 4/31 (2006.01) the total battery cell weight. 280 g 282 Patent Application Publication Mar. 2, 2017 Sheet 1 of 12 US 2017/0062869 A1 Cathode current Anode current collector (e.g. collector (e.g. Al foil) Cu foil) Anode active sS Cathode active material layer . material layer (e.g. (e.g. Si coating) LiCoO2 coating) Pofous separator Anode current FIG. 1(A) prior art collector (e.g. Culfoil) Cathode current collector (e.g. A foil) Cathode active material layer (e.g. Anode active LiCoO2 particles) material layer (e.g. SnO2 Porous particles) separator FIG. 1 (B) prior art Patent Application Publication Mar. 2, 2017. Sheet 2 of 12 US 2017/0062869 A1 240 242 - (0.000000 ---00---00---- ------------ d4-s-s---0-4. {---------000 ab-------00 Patent Application Publication Mar. 2, 2017. Sheet 3 of 12 US 2017/0062869 A1 272 ------------ ------------ 274 -----4--------- 448-4.800-4- d--00-00--d--d FIG. 1(E) Patent Application Publication Mar. 2, 2017. Sheet 4 of 12 US 2017/0062869 A1 Patent Application Publication Mar. 2, 2017. Sheet 5 of 12 US 2017/0062869 A1 These 5 sheets of thin, porous 2D structure are merged or connected at their ends 5 sheets of chicken wire-shaped metal web (thin, porous 2D structure) properly spaced F.G. 3 Patent Application Publication Mar. 2, 2017 Sheet 6 of 12 US 2017/0062869 A1 gxixe: graphite ::::::: 88:8; graxite x.8. 8. &raphite *:::::::::::::: 8xxxxx 8. {.. :xxxii:8:38::ite {{838 worris, s w {}} x38x: g:::::888 giate:8 ; : {{: 88: 8: 8xxxxix: graxite takes {x : x is ex-i:8sity s: O. A Patent Application Publication Mar. 2, 2017 Sheet 7 of 12 US 2017/0062869 A1 Graphene planes intercatant c Intercalation a or b 8 Crystallite > s.A 10 Particles of Length/width 29 Graphite intercalation Natural graphite 102 Compound (GIC) Therma exfoliatio aware esses a m k re- Y W * w f w w w Compression 3. I & w s : s y was * tY s A. ' Y s ws 106 Flexible graphite foil Y p or w * s Air milling res low intensity) osal|Graphitewe was a 08 u- WS As Expanded graphite 3-layer Flakes (t Y 100 nm) graphere trasonication (High intensity) Paper-making or vacuum-assisted filtration S (Nr. Single-layer t graphemeaver 10 Graphite paperim at 2 Graphene (NGP) Paper-making or vacuum-assisted filtration r- is re-C re es secs re 14 Graphene paper/film?membrane FIG. 4 (B) Patent Application Publication Mar. 2, 2017 Sheet 8 of 12 US 2017/0062869 A1 T-Graphite/LFP-conventional-gravimetric E-Graphite|FP conventional-voltmetric an are Graphite/FP-inventive-gravimetric " O an eras SSS 3 sA Sl 3 . 2 EE sO Gravimetric energy (Wh/kg) or Volumetric energy (Wh/l) F.G. 5 Patent Application Publication Mar. 2, 2017 Sheet 9 of 12 US 2017/0062869 A1 aOn-Sifico O2-Conventional-Gravimetric al-Si/LiCoO2-conventionai-Volumetric hy o are SifiCoO2-inventive-Gravimetric ax-Sifico O2-inventive-Volumetric S O S2 e E O 00 O OOO Gravimetric energy (Wh/kg) or Volumetric energy (Wh/l.) F.G. 6 Patent Application Publication Mar. 2, 2017. Sheet 10 of 12 US 2017/0062869 A1 ada if i2C6O6-Conventional-Gravimetric sailifi2C606-conventionai-Volumetric his e amatifi2C6O6-inventive-Gravimetric s S. --if i2C606-inventive-Wolumetric S G G O S. See e . O 1000 Gravimetric energy (Wh/kg) or Volumetric energy (Wh/) F.G. 7 Patent Application Publication Mar. 2, 2017. Sheet 11 of 12 US 2017/0062869 A1 . .0 Gravimetric, Li-MnO2, Conventional one Gravimetric, Li-MnO2 - inventive • a Volumetric-li-MnO2-conventional has OO O wnxm Wometric-i-MnO2- inventive txx O X N C s 8 00 St. t 600 e U 400 8 200 SO 200 250 300 Electrode thickness (um) FG.8 Patent Application Publication Mar. 2, 2017. Sheet 12 of 12 US 2017/0062869 A1 0 Gravimetric-Gr/NMC-conventional ho Gravimetric-Gr/NMC-inventive O s 10 O O S. Volumetric-Gr/NMC-conventional-- N X Volumetric-Gr/NMC-inventive s 800 ch 2 y C (s s ch ( C S. has ad E 2 OO o (s O O% 20% 40% 60% 80% Weight% of Active Materials in a Cell F.G. 9 US 2017/0062869 A1 Mar. 2, 2017 RECHARGEABLE LITHIUM BATTERIES (typically 150-220 Wh/kg and 450-600 Wh/L) and low HAVING ANULTRA-HIGHVOLUMETRIC power densities (typically <0.5 kW/kg and <1.0 kW/L), all ENERGY DENSITY AND REQUIRED based on the total battery cell weight or volume. PRODUCTION PROCESS 0005. The emerging EV and renewable energy industries demand the availability of rechargeable batteries with a FIELD OF THE INVENTION significantly higher gravimetric energy density (e.g. 0001. The present invention relates generally to the field demanding>250 Wh/kg and, preferably, >300 Wh/kg) of lithium batteries, including rechargeable lithium metal and higher power density (shorter recharge times) than what batteries and lithium-ion batteries. the current Li ion battery technology can provide. Further more, the microelectronics industry is in need of a battery BACKGROUND OF THE INVENTION having a significantly larger Volumetric energy density (>650 Wh/L, preferably >750 Wh/L) since consumers 0002 Historically, today's most favorite rechargeable demand to have Smaller-volume and more compact portable energy storage devices—lithium-ion batteries—actually devices (e.g. Smart phones and tablets) that store more evolved from rechargeable “lithium metal batteries' using energy. These requirements have triggered considerable lithium (Li) metal or Li alloy as the anode and a Li research efforts on the development of electrode materials intercalation compound as the cathode. Li metal is an ideal with a higher specific capacity, excellent rate capability, and anode material due to its light weight (the lightest metal), good cycle stability for lithium ion batteries. high electronegativity (-3.04 V vs. the standard hydrogen 0006. Several elements from Group III, IV, and V in the electrode), and high theoretical capacity (3,860 mAh/g). periodic table can form alloys with Li at certain desired Based on these outstanding properties, lithium metal batter Voltages. Therefore, various anode materials based on Such ies were proposed 40 years ago as an ideal system for high elements and some metal oxides have been proposed for energy-density applications. During the mid-1980s, several lithium ion batteries. Among these, silicon has been recog prototypes of rechargeable Li metal batteries were devel nized as one of the next-generation anode materials for oped. A notable example was a battery composed of a Li high-energy lithium ion batteries since it has a nearly 10 metal anode and a molybdenum Sulfide cathode, developed times higher theoretical gravimetric capacity than graphite by MOLI Energy, Inc. (Canada). This and several other 3.590 mAh/g based on LizsSi vs.