IP Library › Granted Patent US 12,738,482
Granted Patent B2
US 12,738,482 · App. 18/751,513 · Granted Sep 15, 2026

Electroactive materials for metal-ion batteries

Inventors: Charles A. Mason (Abingdon, GB); Richard Gregory Taylor (Sully, GB); Christopher Michael Friend (Long Wittenham, GB)
Assignee: Nexeon Limited
H01M4/366H01M4/386H01M4/625H01M10/0525H01M2004/021H01M2004/025
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Quick Facts
Patent No.
US 12,738,482
App. No.
18/751,513
Granted
Sep 15, 2026
Kind
B2
Abstract

The invention relates to a particulate material comprising a plurality of composite particles, wherein the composite particles comprise: (a) a porous carbon framework comprising micropores and mesopores having a total pore volume of at least 0.6 cm 3 /g, where the volume fraction of micropores is in the range from 0.1 to 0.9 and the volume fraction of pores having a pore diameter no more than 20 nm is at least 0.75, and the porous carbon framework has a D 50 particle size of less than 20 μm; (b) silicon located within the micropores and/or mesopores of the porous carbon framework in a defined amount relative to the volume of the micropores and/or mesopores.

Claims (56)

1 . A particulate material comprising a plurality of composite particles, wherein the composite particles comprise:

(a) a porous carbon framework comprising micropores and mesopores, wherein

(i) the micropores and mesopores have a total pore volume as measured by gas adsorption of P 1 cm 3 /g, wherein P 1 has a value of at least 0.6 and no more than 1.6,

(ii) the volume fraction of micropores (φ a ) is in the range from 0.45 to 0.85, based on the total volume of micropores and mesopores;

(iii) the volume fraction of pores having a pore diameter of no more than 20 nm (φ 20 ) is at least 0.8, based on the total volume of micropores and mesopores;

(b) a plurality of nanoscale elemental silicon domains located within the micropores and/or mesopores of the porous carbon framework;

wherein the weight ratio of silicon to the porous carbon framework in the composite particles is in the range from [1×P 1 to 1.9×P 1 ]:1,

wherein the particulate material has a Z value of no more than 10% as determined by TGA analysis in air,

wherein Z=1.875×[(M f −M 800 )/M f ]×100%,

wherein M f is the mass of the TGA sample at completion of oxidation and M 800 is the mass of the TGA sample at 800° C.;

wherein the composite particles have a BET surface area of no more than 60 m 2 /g; and

wherein the composite particles have a D 50 particle diameter in the range from 0.5 to 20 μm.

2 . The particulate material according to claim 1 , wherein P 1 has a value of at least 0.65.

3 . The particulate material according to claim 1 , wherein P 1 has a value of no more than 1.5.

4 . The particulate material according to claim 1 , wherein the volume fraction of micropores is in the range from 0.55 to 0.8, based on the total volume of micropores and mesopores.

5 . The particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework in the composite particles is at least the value given by [φ b +0.75]×P 1 , wherein φ b represents the volume fraction of mesopores, based on the total volume of micropores and mesopores.

6 . The particulate material according to claim 5 , wherein the weight ratio of silicon to the porous carbon framework in the composite particles is at least the value given by [φ b +1]×P 1 .

7 . The particulate material according to claim 6 , wherein the weight ratio of silicon to the porous carbon framework in the composite particles is at least the value given by [φ b +1.1]×P 1 .

8 . The particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework in the composite particles is no more than the value given by [φ b +1.6]×P 1 .

9 . The particulate material according to claim 8 , wherein the weight ratio of silicon to the porous carbon framework in the composite particles is no more than the value given by [φ b +1.5]×P 1 .

10 . The particulate material according to claim 1 , wherein the weight ratio of silicon to the porous carbon framework in the composite particles is at least 1.15×P 1 .

11 . The particulate material according to claim 1 , wherein the volume fraction of pores having a pore diameter of no more than 20 nm (φ 20 ) is at least 0.85, based on the total volume of micropores and mesopores.

12 . The particulate material according to claim 1 , wherein the volume fraction of pores having a pore diameter of no more than 10 nm (φ 10 ) is or at least 0.8, based on the total volume of micropores and mesopores.

13 . The particulate material according to claim 1 , wherein the volume fraction of pores having a pore diameter of no more than 5 nm (φ 5 ) is at least 0.75, based on the total volume of micropores and mesopores.

14 . The particulate material according to claim 1 , wherein the porous carbon framework is a hard carbon framework or a soft carbon framework.

15 . The particulate material according to claim 1 , wherein the porous carbon framework comprises from 50% to 98% sp 2 hybridised carbon as measured by XPS.

16 . The particulate material according to claim 1 , wherein the porous carbon framework is obtained by the pyrolysis of plant biomass.

17 . The particulate material according to claim 1 , wherein the composite particles have a D 50 particle diameter of at least 2 μm and no more than 16 μm.

18 . The particulate material according to claim 1 , wherein the composite particles have a D 10 particle diameter of at least 0.5 μm and a D 90 particle diameter of no more than 30 μm.

19 . The particulate material according to claim 1 , wherein the composite particles have a particle size distribution span of 3 or less.

20 . The particulate material according to claim 1 , wherein the composite particles have a BET surface area of no more than 30 m 2 /g.

21 . The particulate material according to claim 1 , wherein the composite particles have a BET surface area of at least 1 m 2 /g and no more than 40 m 2 /g.

22 . The particulate material according to claim 1 , having specific capacity on lithiation of 1400 to 2340 mAh/g.

23 . The particulate material according to claim 1 , wherein at least 95 wt % of the silicon mass in the composite particles is located within the internal pore volume of the porous carbon framework.

24 . The particulate material according to claim 1 , wherein Z is no more than 5%.

25 . A composition comprising The particulate material as defined in claim 1 and at least one other component selected from: (i) a binder; (ii) a conductive additive; and (iii) an additional particulate electroactive material.

26 . The composition according to claim 25 , wherein the at least one additional particulate electroactive material is selected from graphite and hard carbon.

27 . An electrode comprising the particulate material according to claim 1 in electrical contact with a current collector.

28 . A rechargeable metal-ion battery comprising:

(i) an anode, wherein the anode comprises the electrode according to claim 27 ;

(ii) a cathode comprising a cathode active material capable of releasing and reabsorbing metal ions; and

(iii) an electrolyte between the anode and the cathode.

29 . A particulate material comprising a plurality of composite particles, wherein the composite particles comprise:

(a) a porous carbon framework comprising micropores and mesopores, wherein

(i) the micropores and mesopores have a total pore volume as measured by gas adsorption of P 1 cm 3 /g, wherein P 1 has a value of at least 0.65 and no more than 1.3,

(ii) the volume fraction of micropores (φ a ) is in the range from 0.5 to 0.8, based on the total volume of micropores and mesopores; and

(iii) the volume fraction of pores having a pore diameter of no more than 5 nm (φ 5 ) is at least 0.85, based on the total volume of micropores and mesopores;

(b) a plurality of nanoscale elemental silicon domains located within the micropores and/or mesopores of the porous carbon framework;

wherein the weight ratio of silicon to the porous carbon framework in the composite particles is in the range from [1.1×P 1 to 1.9×P 1 ]:1,

wherein the particulate material has a Z value of no more than 10% as determined by TGA analysis in air,

wherein Z=1.875×[(M f −M 800 )/Mt]×100%,

wherein M f is the mass of the TGA sample at completion of oxidation and M 800 is the mass of the TGA sample at 800° C.;

wherein the composite particles have a BET surface area of no more than 25 m 2 /g; and

wherein the composite particles have a D 50 particle diameter in the range from 1 to 12 μm.

30 . The particulate material according to claim 29 , wherein the volume fraction of micropores (φ a ) is in the range from 0.6 to 0.8, based on the total volume of micropores and mesopores.

31 . The particulate material according to claim 29 , wherein Z is no more than 5%.

Assignments (2)
NUNC PRO TUNC ASSIGNMENT Recorded Jun 24, 2024
From: MASON, CHARLES A.; FRIEND, CHRISTOPHER MICHAEL
To: NEXEON LIMITED
Reel/Frame 067811/0495 →
NUNC PRO TUNC ASSIGNMENT Recorded Jun 24, 2024
From: TAYLOR, RICHARD GREGORY
To: NEXEON LIMITED
Reel/Frame 067811/0571 →
Priority Claims (2)
GB 1820695 · Dec 19, 2018 · national
GB 1912991 · Sep 9, 2019 · national
Continuity (3)
Continuation 17416162 · Dec 19, 2019
Continuation 16274187 · Feb 12, 2019
Related Publication 20250174636A1 · May 29, 2025
References Cited (123)
US 5624606A · Wilson et al. · 1997 [cited by applicant]
US 5798137A · Lord et al. · 1998 [cited by applicant]
US 7361431B2 · Kim et al. · 2008 [cited by applicant]
US 7722991B2 · Zhang et al. · 2010 [cited by applicant]
US 8057900B2 · Luhrs et al. · 2011 [cited by applicant]
US 8361659B2 · Richard · 2013 [cited by applicant]
US 8562869B2 · Mah et al. · 2013 [cited by applicant]
US 8673502B2 · Petrat et al. · 2014 [cited by applicant]
US 8778541B2 · Yamamoto et al. · 2014 [cited by applicant]
US 8906555B2 · Hwang et al. · 2014 [cited by applicant]
US 8945431B2 · Schulz et al. · 2015 [cited by applicant]
US 9039939B2 · Sano · 2015 [cited by applicant]
US 9373838B2 · Yushin et al. · 2016 [cited by applicant]
US 9593413B2 · Amine et al. · 2017 [cited by applicant]
US 9876221B2 · Kim et al. · 2018 [cited by applicant]
US 9997784B2 · Su et al. · 2018 [cited by applicant]
US 10000425B2 · Le Costaouec et al. · 2018 [cited by applicant]
US 10128490B2 · Lee et al. · 2018 [cited by applicant]
US 10147950B2 · Sakshaug et al. · 2018 [cited by applicant]
US 10170753B2 · Ren et al. · 2019 [cited by applicant]
US 10424786B1 · Mason et al. · 2019 [cited by applicant]
US 10508335B1 · Yilmaz et al. · 2019 [cited by applicant]
US 10658659B1 · Mason et al. · 2020 [cited by applicant]
US 10938027B2 · Mason et al. · 2021 [cited by applicant]
US 11011748B2 · Mason et al. · 2021 [cited by applicant]
US 11165054B2 · Mason et al. · 2021 [cited by applicant]
US 12021227B2 · Mason · 2024 [cited by examiner]
US 12176521B2 · Mason · 2024 [cited by examiner]
US 12218341B2 · Mason · 2025 [cited by examiner]
US 20060057355A1 · Suzuki et al. · 2006 [cited by applicant]
US 20110200874A1 · Ono et al. · 2011 [cited by applicant]
US 20110309310A1 · Koller et al. · 2011 [cited by applicant]
US 20120156493A1 · Maisels et al. · 2012 [cited by applicant]
US 20120264020A1 · Burton et al. · 2012 [cited by applicant]
US 20130209348A1 · Ludvik et al. · 2013 [cited by applicant]
US 20130280601A1 · Geramita et al. · 2013 [cited by applicant]
US 20130344391A1 · Yushin et al. · 2013 [cited by applicant]
US 20140057179A1 · Yushin et al. · 2014 [cited by applicant]
US 20140272592A1 · Thompkins et al. · 2014 [cited by applicant]
US 20150303458A1 · Guo et al. · 2015 [cited by applicant]
US 20150321920A1 · Geramita et al. · 2015 [cited by applicant]
US 20160104882A1 · Yushin et al. · 2016 [cited by applicant]
US 20160298234A1 · Yang · 2016 [cited by applicant]
US 20160351894A1 · Wagner et al. · 2016 [cited by applicant]
US 20170092950A1 · Xiao et al. · 2017 [cited by applicant]
US 20170170477A1 · Sakshaug et al. · 2017 [cited by applicant]
US 20170301917A1 · Yuge · 2017 [cited by applicant]
US 20170346084A1 · Sakshaug · 2017 [cited by applicant]
US 20180151884A1 · Yushin et al. · 2018 [cited by applicant]
US 20180331356A1 · Feaver et al. · 2018 [cited by applicant]
US 20180342732A1 · Troegel et al. · 2018 [cited by applicant]
CN 102214817A · 2011 [cited by applicant]
CN 102456876A · 2012 [cited by applicant]
CN 104577084A · 2015 [cited by applicant]
CN 105489891A · 2016 [cited by applicant]
CN 103840140B · 2017 [cited by applicant]
CN 107425180A · 2017 [cited by applicant]
CN 107863513A · 2018 [cited by applicant]
CN 108428876A · 2018 [cited by applicant]
CN 109004203A · 2018 [cited by applicant]
DE 102014211012A1 · 2015 [cited by applicant]
EP 3086388B1 · 2018 [cited by applicant]
JP 2003100284A · 2003 [cited by applicant]
JP 4069465B2 · 2008 [cited by applicant]
JP 5647366B1 · 2014 [cited by applicant]
JP 6167127B2 · 2017 [cited by applicant]
JP 6451340B2 · 2019 [cited by applicant]
KR 20160126857A · 2011 [cited by applicant]
KR 101665099B1 · 2016 [cited by applicant]
KR 20180024922A · 2018 [cited by applicant]
KR 20180078176A · 2018 [cited by applicant]
KR 101898110B1 · 2018 [cited by applicant]
WO 200227822A1 · 2002 [cited by applicant]
WO 2012097969A1 · 2012 [cited by applicant]
WO 2012131628A1 · 2012 [cited by applicant]
WO 2016116323A1 · 2016 [cited by applicant]
WO 2017040299A1 · 2017 [cited by applicant]
WO 2018165610A1 · 2018 [cited by applicant]
WO 2018166735A1 · 2018 [cited by applicant]
Copending U.S. Appl. No. 17/316,908, filed May 11, 2021. [cited by applicant]
Copending U.S. Appl. No. 17/292,241, filed May 7, 2021. [cited by applicant]
Copending U.S. Appl. No. 17/292,262, filed May 7, 2021. [cited by applicant]
Copending U.S. Appl. No. 17/416,671, filed Jun. 18, 2021. [cited by applicant]
Copending U.S. Appl. No. 17/190,024, filed Mar. 2, 2021. [cited by applicant]
Sugiyama K et al., “Pulse Chemical Vapour Infiltration of SiC in Porous Carbon or SiC Particulate Preform Using an R. F. Healing System,” J. Materials Sci., 25(10), 4511-17 (1990). [cited by applicant]
International Search Report in International Patent Application PCT/GB2019/053640, dated Feb. 20, 2020. [cited by applicant]
Malvern Instruments, “A Basic Guide to Particle Size Characterization,” May 2012. [cited by applicant]
R. Zhang et al., “Highly Reversible and Large Lithium Storage in Mesoporous Si/C Nanocomposite Anodes with Silicon Nanoparticles Embedded in a Carbon Framework,” Adv. Materials, 26(39), 6749-55 (2014). [cited by applicant]
Bardet et al., “In situ investigation of mesoporous silicon oxidation kinetics using infrared emittance spectroscopy,” Phys. Chem. Chem. Phys., 18, 18201-308 (2016). [cited by applicant]
Cadore! et al., “Silicon Chemical Vapor Deposition on macro and submicron powders in a fluidized bed,” Powder Technology, 190(102), 185-91 (2009). [cited by applicant]
Coppey et al., “Decorated carbon nanolubes by silicon deposition in fluidized bed for Li-ion battery anodes,” Chem. Eng. Res. Des. 91, 2491-96 (2013). [cited by applicant]
Curdls et al., “Upscaling the chemical vapour infiltration process of activated carbon with TMS,” Physics Procdia, 46, ) 48-54 (2013). [cited by applicant]
Wilson et al., “Lithium Insertion in Carbons Conalining Nanodispersed Silicon,” J_ Electrochem. Soc., 142(2), 326-332 1995). [cited by applicant]
Delhaes, “Chemical vapor deposition and infiltration processes of carbon materials,” Carbon, 40, 641-657, (2002). [cited by applicant]
Holzapfel et al., “A new type of nano-sized silicon/carbon composite electrode for reversible lithium insertion,” Chem.:; ommun., 1566-68 (2005). [cited by applicant]
Holzapfel et al., “Chemical Vapor Deposited Silicon/Graphite Compound Material as Negative Electrode for Lithium-Ion Batteries,” Electrochem. And Sol. State Lett., 8(10), A516-520 (2005). [cited by applicant]
Holzapfel et al., “Nano silicon for lithium-ion batteries,” Electrochem. Acta, 52, 973-78 (2006). [cited by applicant]
Jaumann et al., “Dichlorosilane-Derived Nano-Silicon inside Hollow Carbon Spheres as High-Performance Anode in Li Ion Batteries,” J. Maler. Chem. A, 5, 9262-9271 (2017). [cited by applicant]
Jaumann et al., “SEI-componenl formation on sub 5 nm sized silicon nanoparticles in Li-ion batteries: the role of eleclrode preparation, FEC addition and binders,” Phys. Chem. Chem. Phus., 17(38), 24956-67 (2015). [cited by applicant]
Kaae, J. L., “Coaling of small particles by chemical vapor deposition while the particles are fluidized,” Mal. Res. Soc. Symp. Proc. 372, 139 (1995). [cited by applicant]
Krzeminski et al., Silicon dry oxidation kinetics at low temperature in the nanomelric range: modeling and experiment, arXiv:1106.3160v1, available at https://arxiv.org/pdf/1106.3160v1 .pdf, 54 pages (2011 ). [cited by applicant]
Magasinksi et al., “High-performance lithium-ion anodes using a hierachical bottom-up approach,” Nature Materials, 9 4), 352-58 (2010). [cited by applicant]
Kouadri-Moslefa et al., “Silicon Chemical Vapor Deposition {CVD) on microporous powders in a fluidized bed,” Powder Technology, 120, 82-87 (2001). [cited by applicant]
Pflitsch et al., “Chenmical vapor infiltration of activated carbon with tetramethylsilale,” Carbon, 79(1), 28-35 (2014). [cited by applicant]
Reuge et al., “Modeling of Silicon CVD into Agglomerates of Sub/micromelersiz Particles in a Fluidized Bed,” Chem. Vap. Deposition 17, 305-311 (2011). [cited by applicant]
Saito et al., “Solution combustion synthesis of porous Sn—C composite as anode material for lithium ion batteries,” Adv Powder. Tech., 27, 1730-37 (2016). [cited by applicant]
Vahlas et al., “Principles and applications of CVD powder technology,” Mat. Sci. and Eng., R53, 1-72 (2006). [cited by applicant]
Wang et al., “Chemical vapor deposition and atomic layer deposition for advanced lithium ion batteries and, upercapacitors,” Energy & Env. Sci., 8, 1889-2014 (2015). [cited by applicant]
Wang et al., “Facile Preparation of Hierarchically Porous Carbon Monoliths with Well-Ordered Mesostructures,” Chem. Mater., 18, 6373-6381 (2006). [cited by applicant]
Wang et al., “Synthesis of monolithic 3D ordered macroporous carbon/nano-silicon composites by diiodosilane decomposition,” Carbon, 46, 1702-1710 (2008). [cited by applicant]
Wilson et al., “Carbonaceous Materials Containing Silicon As Anodes For Lithium-Ion Cells,” Mat. Res. Soc. Symp. Proc., vol. 393, 305 (1995). [cited by applicant]
Wilson et al., “Nanodispersed silicon in pregraphitic Carbons,” J. Appl. Lett. Phys., 77, 2363-69 (1995). [cited by applicant]
Yano et al. “Novel method to incorporate Si into monodispersed mesoporous carbon spheres,” J. Colloid and Int. Sci., 479, 20-24 (2016). [cited by applicant]
Yano et al., “Incorporation of silicon into monodispersed starburst carbon spheres with LVD method,” Microporous and Mesoporous Mat., 247, 46-51 (2017). [cited by applicant]
Zhang et al., “Tin-Nanoparticles Encapsulated in Elastic Hollow Carbon Spheres,” Adv. Mater. 20, 1160-1165 (2008). [cited by applicant]
Search and Examination Report issued in co-pending Great Britain Patent Application No. GB1818232.9, dated Dec. 24, 2018, 9 pages. [cited by applicant]
Search and Examination Report issued in co-pending Great Britain Patent Application No. GB1818235.2, dated Dec. 24, 2018, 9 pages. [cited by applicant]
Search and Examination Report issued in co-pending Great Britain Patent Application No. GB1820736.5, dated Jan. 9, 2019, 9 pages. [cited by applicant]
Search and Examination Report issued in co-pending Great Britain Patent Application No. GB1820742.3, dated Jan. 9, 2019, 9 pages. [cited by applicant]
Co-Pending U.S. Appl. No. 16/247,182, filed Feb. 12, 2019. [cited by applicant]
Co-Pending U.S. Appl. No. 16/274,185, filed Feb. 12, 2019. [cited by applicant]
Co-Pending U.S. Appl. No. 16/275,246, filed Feb. 13, 2019. [cited by applicant]
Extended European Search Report dated Oct. 14, 2025 for corresponding EP Application No. 25166630.1 (10 pages). [cited by applicant]